Automatic dishwashing compositions and methods for use with electrochemical cells and/or electrolytic devices

ABSTRACT

The present invention relates to automatic dishwashing detergent compositions and methods of using compositions comprising halogenated salts, phosphate and/or silicate in conjunction with electrolyzed water in automatic dishwashing appliances comprising an electrochemical cell and/or electrolytic device for treating tableware to improve cleaning, sanitizing and stain removal by controlling hardness, corrosion and dispersancy.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit of the filing date of U.S.Provisional Application Nos. 60/381,473; 60/381,455; 60/381,472;60,381,146 and all filed May 17, 2002. This application claims referenceto U.S. Provisional Application No. 60/280,913, filed Apr. 2, 2001 andU.S. patent application Ser. No. 09/947,846, filed Sep. 6, 2001.

FIELD OF THE INVENTION

[0002] The present invention relates to automatic dishwashing detergent(ADD) compositions and methods of using compositions comprisinghalogenated salts, phosphate, and/or silicate in conjunction withelectrolyzed water in automatic dishwashing appliances comprising anelectrochemical cell and/or electrolytic device for treating tablewareto improve cleaning, sanitizing and stain removal by controllinghardness, corrosion and dispersancy.

BACKGROUND OF THE INVENTION

[0003] Electrochemical cells for use in automatic dishwashing appliancesare designed to operate by making use of the water electrolysis processwherein, at the anode-water interface, OH− being present in water due toelectrolytic dissociation of water molecules donates an electron to theanode and can be thereby oxidized to oxygen gas which can be removedfrom the system. As a result, the H+ concentration can be enhanced atthe anode-water interface so that H+ enriched acidic water can beproduced. In a similar manner, at the cathode-water interface, H+accepts an electron from the cathode and can be reduced to hydrogen toform hydrogen gas which can be similarly eliminated from the system sothat the OH− concentration can be increased at the cathode-waterinterface whereby OH− enriched alkaline water can be generated. Further,when a halogen-containing water (such as, natural water containingsodium chloride or an aqueous solution of sodium chloride) can besubjected to electrolysis, halogenated mixed oxidants are generated inthe electrolyzed water.

[0004] The following references disclose use of electrochemical cells:U.S. Pat. No. 5,932,171; U.S. Pat. No. 4,481,086; U.S. Pat. No.4,434,629; U.S. Pat. No. 4,493,760; U.S. Pat. No. 4,402,197; U.S. Pat.No. 5,250,160; U.S. Pat. No. 5,534,120; U.S. Pat. No. 5,865,966; U.S.Pat. No. 5,947,135; JP Application No. 10057297A; JP Application No.10179489A; JP Application No. 10033448A; JP Patent No. 09122060; JPPatent No. 2000116587; JP Patent No. 10178491; and EP Application No.0983806A1.

[0005] The following references are also related to electrolyzed water:U.S. Pat. No. 3,616,355; U.S. Pat. No. 4,048,047; U.S. Pat. No.4,062,754; U.S. Pat. No. 4,100,052; U.S. Pat. No. 4,328,084; U.S. Pat.No. 4,761,208; U.S. Pat. No. 5,314,589; U.S. Pat. No. 5,395,492; U.S.Pat. No. 5,439,576; U.S. Pat. No. 5,954,939 (equiv. EP 711,730); and WO00/34184.

[0006] A problem associated with using an automatic dishwashingappliance containing an electrochemical cell and/or electrolytic device(hereinafter “cell and/or device”) to produce electrolyzed water forcleaning tableware in the absence of a specific ADD composition can bethat there can be a potential for serious consumer dissatisfaction withthe performance results. While use of electrolyzed waster alone providesa source of alkalinity and bleaching agent, it nonetheless lacks theability to control hardness, dispersancy and/or corrosion, and thereforecan result in unsatisfactory performance. Though some of the referencesdisclose the use of detergent ingredients in conjunction withelectrolyzed water, they are either not related to treating tableware inautomatic dishwashing applications and/or do not provide for the controlof hardness, dispersancy and/or corrosion required by the presentinvention.

[0007] U.S. Pat. No. 5,932,171 discloses a phosphate can be used inconjunction with electrolyzed water for sterilizing medical instrumentsin an immersive-type sterilization bath, but does not disclose orsuggest the use of phosphate in an ADD composition in conjunction withelectrolyzed water to control hardness, dispersancy and/or corrosion.Furthermore, this reference broadly discloses the use of electrolyzedwater in conjunction with an “anticorrosive,” but fails to disclosespecific anticorrosives (such as silicates, which are some of the mostwell known anticorrosives) or other “buffer additives.”

[0008] Similarly, U.S. Pat. No. 5,250,160 discloses a phosphate can beused in conjunction with electrolyzed water for sterilizing objects inan immersive-type sterilization bath, but does not disclose or suggestthe use of phosphate in an ADD composition for building and/or cleaningpurposes, or to control hardness, dispersancy and/or corrosion. Althoughthis reference generally describes the use of electrolyzed water inconjunction with simple phosphates, the function of the phosphatedisclosed by the reference can be simply to provide electrolytes to aidin the process of electrolysis.

[0009] JP Application No. 10179489A describes the use of detergent inconjunction with electrolyzed water but specifically teaches that thebest mode reduces or abolishes the need for a detergent. U.S. Pat. No.4,402,197 states the use of a detergent that “has a simplifiedformulation” but provides no details other than it could include anenzyme system. Similarly, the following references do not discloseelectrolyzed water in conjunction with an ADD composition to controlhardness, dispersancy and/or corrosion. JP Application No. 10057297Adescribes the use of a detergent but gives no specifics. JP ApplicationNo. 10033448A also broadly describes the use of “a detergent” and “analkaline detergent” but provides no specifics. None of theabovementioned references disclose the benefits of hardness, dispersancyand/or corrosion control when treating tableware with electrolyzed waterin conjunction with a specific ADD composition, as disclosed in thepresent application.

[0010] There remains a need to provide a specific ADD composition and amethod of using a specific ADD composition in conjunction withelectrolyzed water for treating tableware in an automatic dishwashingappliance for controlling hardness, corrosion and dispersancy in orderto improve cleaning, sanitizing and stain removal performance.

[0011] It has now been surprisingly discovered that using electrolyzedwater in conjunction with an ADD composition comprising a halogenatedsalt and a builder, such as phosphate and/or silicate, completes theportfolio of cleaning chemistry that can be necessary for a robust andsatisfactory automatic dishwashing end result. The present inventionmeets this need by providing a unique halogenated mixed oxidant cleaningsystem. According to this invention, superior tableware cleaning,sanitizing and stain removal can be achieved when alkalinity forbleaching/sanitization can be provided by electrolyzed water, hardnesscontrol can be provided by phosphate and anticorrosion benefits areprovided by silicates.

[0012] Electrolyzed water when combined with a builder, such as aphosphate and/or silicate, in the presence of a halogenated salt, can beparticularly effective in removing a wide range of soils,microorganisms, and/or stains from soiled tableware. This combinationwill also allow ADD compositions to be sold without bleach, a distinctadvantage over the prior art, while at the same time providing thecleaning performance of a powdered automatic dishwashing detergentcomposition that contains both enzyme and bleach. As a result,non-bleach-containing, enzyme-based liquid-gel automatic dishwashingdetergent compositions could become a consumer-preferred ADDcomposition.

SUMMARY OF THE INVENTION

[0013] In one aspect of the present invention, an automatic dishwashingcomposition for treating tableware in an automatic dishwashing appliancecan comprise an electrochemical cell and/or electrolytic device forimproved tableware cleaning, sanitizing, and/or stain removal, thecomposition comprising: (a) a halogen dioxide salt having the formula(M)_(x)(XO₂)_(y), wherein X can be Cl, Br, or I and wherein M can be ametal ion or cationic entity, and wherein x and y are chosen such thatthe salt can be charge balanced; and (b) a component selected from thegroup consisting of a builder, suds suppressor, perfume, enzyme,bleach-scavenging agent, a metal-protecting agent, and mixtures thereof;wherein the composition can be optionally free of bleach.

[0014] In another aspect of the present invention, an automaticdishwashing composition for treating tableware in an automaticdishwashing appliance can comprise an electrochemical cell and/orelectrolytic device for improved tableware cleaning, sanitizing, and/orstain removal, the composition comprising: (a) at least about 0.1%, byweight of the composition, of a halogenated salt having the formula(M)_(x)(X)_(y), wherein X can be Cl, Br, or I and wherein M can be ametal ion or cationic entity, and wherein x and y are chosen such thatthe salt can be charge balanced; and (b) a component selected from thegroup consisting of a builder, suds suppressor, perfume, enzyme,bleach-scavenging agent, a metal-protecting agent, enzymes, and mixturesthereof; wherein the composition can be optionally free of bleach.

[0015] In another aspect of the present invention, a liquid, liquitab,and/or gel automatic dishwashing composition for treating tableware inan automatic dishwashing appliance can comprise an electrochemical cellfor improved tableware cleaning, sanitizing, and/or stain removal, thecomposition comprising: (a) at least about 0.1%, by weight of thecomposition, of a halogenated salt having the formula (M)_(x)(X)_(y),wherein X can be Cl, Br, or I and wherein M can be a metal ion orcationic entity, and wherein x and y are chosen such that the salt canbe charge balanced; (b) a component selected from the group consistingof a builder, suds suppressor, perfume, enzyme, bleach-scavenging agent,a metal-protecting agent, and mixtures thereof; and (c) an effectiveamount of an enzyme; and (d) an effective amount of a thickening agent;wherein the liquid, liquitab, and/or gel composition can be optionallyfree of bleach.

[0016] In another aspect of the present invention, a method of treatingtableware in an automatic dishwashing appliance can comprise anelectrochemical cell that results in improved tableware cleaning,sanitizing, and/or stain removal, the method comprising the steps of:(a) placing tableware in need of treatment in the appliance; (b)providing an automatic dishwashing composition comprising a componentselected from the group consisting of a halogenated salt, builder, sudssuppressor, perfume, bleach-scavenging agent, metal-protecting agent,and mixtures thereof, during a wash and/or a rinse cycle in theappliance; (c) passing an aqueous electrolytic solution through theelectrochemical cell to generate at least some electrolyzed water in thewash and/or rinse liquor of the appliance; and (d) contacting thetableware with the electrolyzed water.

[0017] In another aspect of the present invention, an article ofmanufacture for an automatic dishwashing appliance can comprise: (a) apackage; (b) a replacement product comprising a component selected fromelectrolytic solution comprising halogen ions, halogenated salts havingthe formula (M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y) wherein X can be Cl,Br, or I and wherein M can be a metal ion or cationic entity and whereinx and y are chosen such that the salt can be charge balanced,electrolysis precursor compound, a halogenated salt with low watersolubility, a halogenated salt contained within a medium for controlledrelease, and mixtures thereof; (c) optionally, a a porous basketcomprising the product for dispensing; and (c) information inassociation with the package comprising instructions to insert thereplacement components and/or the a porous basket in the applianceand/or the electrolytic device.

[0018] In yet another aspect of the present invention, an ADDcomposition of matter consists essentially of the in the wash and/orrinse liquor of an automatic dishwashing appliance comprising anelectrochemical cell and/or electrolytic device for improved tablewarecleaning, sanitizing, and/or stain removal, the composition of mattercomprising: (a) at least some electrolyzed water comprising halogenatedmixed oxidants; (b) an ADD composition comprising a compound selectedfrom the group consisting of a halogenated salts, halogenated salt withlow water solubility, builder, suds suppressor, perfume, enzyme,bleach-scavenging agent, a metal-protecting agent, and mixtures thereof;(c) optionally, an ADD composition comprising a compound selected fromthe group consisting of an electrolytic composition comprising halogenions, an electrolytic composition comprising halogenated salts havingthe formula (M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y) wherein X can be Cl,Br, or I and wherein M can be a metal ion or cationic entity and whereinx and y are chosen such that the salt can be charge balanced, anelectrolysis precursor compound, a halogenated salt with low watersolubility, an electrolysis precursor compound contained within a mediumfor controlled release, and mixtures thereof; and (d) optionally, atleast one adjunct ingredient.

[0019] The following description can be provided to enable any personskilled in the art to make and use the invention, and can be provided inthe context of a particular application and its requirements. Variousmodifications to the embodiments will be readily apparent to thoseskilled in the art, and the generic principles defined herein can beapplied to other embodiments and applications without departing from thespirit and scope of the invention. The present invention can be notintended to be limited to the embodiments shown. Thus, since thefollowing specific embodiments of the present invention are intendedonly to exemplify, but in no way limit, the operation of the presentinvention, the present invention can be to be accorded the widest scopeconsistent with the principles, features and teachings disclosed herein.

[0020] It should be understood that every maximum numerical limitationgiven throughout this specification will include every lower numericallimitation, as if such lower numerical limitations were expresslywritten herein. Every minimum numerical limitation given throughout thisspecification will include every higher numerical limitation, as if suchhigher numerical limitations were expressly written herein. Everynumerical range given throughout this specification will include everynarrower numerical range that falls within such broader numerical range,as if such narrower numerical ranges were all expressly written herein.

[0021] The various advantages of the present invention will becomeapparent to those skilled in the art after a study of the foregoingspecification and following claims. The following specific embodimentsof the present invention are intended to exemplify, but in no way limit,the operation of the present invention. All documents cited are, inrelevant part, incorporated herein by reference; the citation of anydocument can be not to be construed as an admission that it can be priorart with respect to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0022] Electrolysis

[0023] Electrodes

[0024] An electrode can generally have any shape that can effectivelyconduct electricity through the aqueous electrolytic solution betweenitself and another electrode, and can include, but can be not limitedto, a planar electrode, an annular electrode, a spring-type electrode,and a porous electrode. The anode and cathode electrodes can be shapedand positioned to provide a substantially uniform gap between a cathodeand an anode electrode pair. On the other hand, the anode and thecathode can have different shapes, different dimensions, and can bepositioned apart from one another non-uniformly. The importantrelationship between the anode and the cathode can be for a sufficientflow of current through the anode at an appropriate voltage to promotethe conversion of the halogenated salt solution to halogenated bleachspecies within the cell passage adjacent the anode.

[0025] Planar electrodes, such as shown, have a length along the flowpath of the solution, and a width oriented transverse to the flow path.The aspect ratio of planar electrodes; defined by the ratio of thelength to the width, can be generally between 0.2 and 10, morepreferably between 0.1 and 6, and most preferably between 2 and 4.

[0026] Another embodiment of the present invention relates to anautomatic dishwashing appliance containing a robust cell and/or device.The robust cell being non-partitioned can be less prone to fouling. Therobust cell can comprise a cathode of stainless steel and an anode oftitanium. The anode can be coated and/or layered with at least one ofthe materials selected from the group consisting of platinum, ruthenium,iridium, and oxides, alloys, and mixtures thereof. The cell passage ofthe robust cell forms a gap between the at least one pair of electrodeshaving a gap spacing between about 0.1 mm to about 0.5 mm; and whereinthe operating voltage can be between about 3 and about 6 volts.

[0027] Porous media useful in the present invention are commerciallyavailable from Astro Met Inc. in Cincinnati, Ohio, Porvair Inc. inHenderson, N.C., or Mott Metallurgical in Farmington, Conn. AlternatelyU.S. Pat. Nos. 5,447,774 and 5,937,641 give suitable examples of porousmedia processing. Preferably, the porous anode, 21a, has a ratio ofsurface area (in square centimeters) to total volume (in cubiccentimeters) of more than about 5 cm⁻¹, more preferably of more thanabout 10 cm⁻¹, even more preferably more than about 50 cm⁻¹ and mostpreferably of more than about 200 cm⁻¹. Preferably the porous anode,21a, has a porosity of at least about 10%, more preferably of about 30%to about 98%, and most preferably of about 40% to about 70%. Preferably,the porous anode has a combination of high surface area and electricalconductivity across the entire volume of the anode, to optimize thesolution flow rate through the anode, and the conversion of halogenatedsalt solution contained in the solution to the halogenated bleachspecies.

[0028] The electrodes are commonly metallic, conductive materials,though non-metallic conducting materials, such as carbon, can also beused. The materials of the anode and the cathode can be the same, butcan advantageously be different. To minimize corrosion, chemicalresistant metals are preferably used. Examples of suitable electrodesare disclosed in U.S. Pat. No. 3,632,498 and U.S. Pat. No. 3,771,385.Preferred anode metals are stainless steel, platinum, palladium,iridium, ruthenium, as well as iron, nickel and chromium, and alloys andmetal oxides thereof. More preferred are electrodes made of a valvemetal such as titanium, tantalum, aluminum, zirconium, tungsten oralloys thereof, which are coated or layered with a Group VIII metal thatcan be preferably selected from platinum, iridium, and ruthenium, andoxides and alloys thereof. One preferred anode can be made of titaniumcore and coated with, or layered with, ruthenium, ruthenium oxide,iridium, iridium oxide, and mixtures thereof, having a thickness of atleast 0.1 micron, preferably at least 0.3 micron.

[0029] For many applications, a metal foil having a thickness of about0.03 mm to about 0.3 mm can be used. Foil electrodes should be madestable in the electrochemical cell so that they do not warp or flex inresponse to the flow of liquids through the passage that can interferewith proper electrolysis operation. The use of foil electrodes can beparticularly advantageous when the cost of cell and/or device should beminimized, or when the lifespan of the electrolysis device can beexpected or intended to be short, generally about one year or less. Foilelectrodes can be made of any of the metals described above, and arepreferably attached as a laminate to a less expensiveelectrically-conductive base metal, such as tantalum, stainless steel,and others.

[0030] The following references are also related to electrodes: U.S.Pat. No. 3,616,355; U.S. Pat. No. 4,048,047; U.S. Pat. No. 4,062,754;U.S. Pat. No. 4,100,052; U.S. Pat. No. 4,328,084; U.S. Pat. No.4,761,208; U.S. Pat. No. 5,314,589; U.S. Pat. No. 5,395,492; U.S. Pat.No. 5,439,576; U.S. Pat. No. 5,954,939 (equiv. EP 711,730); and WO00/34184.

[0031] Electrochemical Cell

[0032] An electrochemical cell can comprise at least one pair ofelectrodes; an anode, and a cathode, defining a cell gap, comprising acell passage, formed therebetween through which the aqueous electrolyticsolution can flow. The electrodes can be held a fixed distance away fromone another by at least one pair of opposed non-conductive electrodeholders having electrode spacers that space apart the confrontinglongitudinal edges of the anode and cathode defines the cell gapcomprising the cell passage. The cell passage has an inlet openingthrough which the aqueous electrolytic solution can pass into of theelectrochemical cell and an opposed outlet opening from which theeffluent can pass out of the electrochemical cell.

[0033] The anode and cathode and the opposed plate holders are heldtightly together between a non-conductive anode cover and cathode coverby a retaining means that can comprise non-conductive, water-proofadhesive, bolts, or other means, thereby restricting exposure of the twoelectrodes only to the aqueous electrolytic solution that flows throughthe passage. The anode lead and cathode lead extend laterally andsealably through channels made in the electrode holders.

[0034] The gap between the at least one pair of electrodes has a gapspacing between about 0.1 mm to about 5.0 mm. The operating voltage thatcan be applied between the at least one pair of electrodes can bebetween about 1 and about 12 volts; preferably between about 3 volts and6 volts. The electrochemical cell can be disposable and/or replaceablevia a refill and/or a replacement cartridge which can be removable fromat least one sealed or sealable compartment of an automatic dishwashingappliance containing an attached, integrated electrochemical cell and/orelectrolytic device.

[0035] The electrochemical cell can also comprise two or more anodes ortwo or more cathodes. The anode and cathode plates are alternated sothat the anode can be confronted by a cathode on each face, with a cellpassage therebetween. Examples of electrochemical cells that cancomprise a plurality of anodes and cathodes are disclosed in U.S. Pat.No. 5,534,120, issued to Ando et al. on Jul. 9, 1996, and U.S. Pat. No.4,062,754, issued to Eibl on Dec. 13, 1977, which are incorporatedherein by reference.

[0036] Generally, the electrochemical cell will have at least one ormore inlet openings in fluid communication with the wash and/or rinseliquor in the appliance. The cell passage can be in fluid communicationwith the inlet openings and at least one outlet opening which can bealso in fluid communication with the wash and/or rinse liquor in theappliance.

[0037] The electrochemical cell can comprise a porous, or flow-throughelectrode comprising a porous cathode and a porous anode. The porousanode has a large surface area and large pore volume sufficient to passthere through a large volume of electrolytic solution. The plurality ofpores and flow channels in the porous anode provide a greatly increasedsurface area providing a plurality of passages, through which theaqueous electrolytic solution can pass.

[0038] The flow path of the aqueous electrolytic solution through aporous anode should be sufficient, in terms of the exposure time of thesolution to the surface of the anode to convert the aqueous electrolyticsolution containing a halogen salt to the halogenated mixed-oxidants.The flow path can be selected to pass the aqueous electrolytic solutionin parallel with the flow of electricity through the porous anode (ineither the same direction or in the opposite direction to the flow ofelectricity), or in a cross direction with the flow of electricity. Theporous anode permits a larger portion of the aqueous electrolyticsolution to pass through the passages adjacent to the anode surface,thereby increasing the proportion of the halogenated salt solution thatcan be converted to the halogenated bleach species.

[0039] Electrolytic Solution

[0040] The components of the aqueous electrolytic solution can beselected from the group consisting of chloride ions, chlorite ions,water-soluble salts having the formula (M)_(x)(XO₂)_(y) and/or(M)_(x)(X)_(y) wherein X can be Cl, Br, or I and wherein M can be ametal ion or cationic entity and wherein x and y are chosen such thatthe salt can be charge balanced, electrolysis precursor compounds,electrolysis salts with low water solubility, electrolysis precursorcompounds contained within a medium or matrix for controlled release,and mixtures thereof.

[0041] Preferred electrolytic solutions contain at least some halogenions, including but not limited to chloride, chlorite, bromide, bromite,iodide, and iodite, and mixtures thereof, preferably chloride ions orchlorite ions. Of course, electrolytic solutions containing higherlevels of halogen ions are more efficiently converted into a dischargeeffluent solution having even larger amounts of the mixed oxidants. Thiscan be due in part because the conductivity of the aqueous electrolyticsolution increases with the concentration of halogen ions, therebyenabling a greater current flow across the passage gap between the pairof electrodes under a constant voltage potential. In general, to producethe same amount of mixed oxidants at a fixed power (current and voltagepotential), an aqueous electrolytic solution having a higherconcentration of halogen ions allows a substantially smaller gapspacing, compared to an aqueous electrolytic solution having lowerconcentrations of the halogen ions.

[0042] Preferably the aqueous electrolytic solution has a specificconductivity ρ of greater than 100 μS/cm, preferably more than 150μS/cm, even more preferably more than 250 μS/cm, and most preferablymore than 500 μS/cm.

[0043] Halogenated Mixed Oxidants

[0044] The chemistry of the conversion of halogen ions to halogenatedmixed oxidants proceeds as electrical energy can be applied between thepair of electrodes and through the aqueous electrolytic solution. Sincechloride in common salt can be the most prevalent halogen available, thedescription of the electrochemical cell chemistry and operation will bedescribed with respect to converting chloride to chlorine, although itshould be understood that other halogen ions (halides and/or halites),especially bromide, iodide, chlorite, bromite, and iodite would functionand respond similarly to chloride. Similarly, since chlorinated tapwater can be a useful electrolytic solution, the description below willdescribe the use of water having a residual amount of chloride ions,although it should be understood that other electrolytic solutions canbe used, preferably those consisting of chloride ions, chlorite ions,water-soluble salts having the formula (M)_(x)(XO₂)_(y) and/or(M)_(x)(X)_(y) wherein X can be Cl, Br, or I and wherein M can be ametal ion or cationic entity and wherein x and y are chosen such thatthe salt can be charge balanced, electrolysis precursor compounds,electrolysis salts with low water solubility, electrolysis precursorcompounds contained within a medium or matrix for controlled release,and mixtures thereof.

[0045] Water containing residual amounts of chloride ions can beelectrolyzed as it passes between the anode (the positively chargedelectrode of the pair) and the cathode (the negatively chargedelectrode). Two of the reactions that occur at the anode electrode areset forth below as equations 1 and 2.

2Cl⁻→Cl₂+2e⁻  (1)

H2O→e 1/2O₂+2H⁺+2e⁻  (2)

[0046] One of the reactions that occurs at the cathode can be set forthas equation 3.

2H₂O+2e−→H₂+2OH⁻  (3)

[0047] Furthermore, chlorine molecules can be converted to hypochlorousacid and hypochlorite ions as set forth in equations 4 and 5,respectively.

Cl₂+H₂O→HOCl+Cl⁻+H⁺  (4)

HOCl→OCI⁻+H⁺  (5)

[0048] The chlorine gas that can be generated dissolves or diffuses intothe water to generate free chlorine in the form of hypochlorous acid,hypochlorous acid ions, and hypochlorite ions. It can be believed thatother various halogenated mixed oxidants that can form include chlorinedioxide (ClO₂), other chloro-oxides molecules, oxide molecules includingozone, hydrogen oxide (H₂O₂) and free radicals (oxygen singlet, hydroxylradicals) and ions thereof. Such halogenated mixed oxidants aredemonstrated and described in U.S. Pat. No. 3,616,355 and U.S. Pat. No.4,761,208. These types of halogenated mixed oxidants are very effectivebiocidal agents, but have very short lifespans, lasting from a fractionof a second to minutes under ordinary, ambient conditions. Consequently,generating these biocidal agents at the point of use ensures the mosteffective use of the biocidal species, such as when generating thebiocidal agents at specific time intervals throughout the wash and/orrinse cycles of the operation of the appliance and/or continuouslywithout regard to sequencing.

[0049] For effective sanitizing treatment of tableware in contact withthe aqueous electrolytic solution, the concentration of halogenatedmixed oxidants in the electrochemical cell effluent, as measured by theDPD method, can be at least about 0.1 mg per liter (about 0.1 ppm) ofelectrochemical cell effluent, preferably at least about 0.2 mg perliter (about 0.2 ppm), more preferably at least about 1 mg per liter(about 1 ppm), and most preferably at least about 5 mg per liter (about5 ppm).

[0050] An important consideration can be the productivity of theelectrical power of the electrochemical cell. When battery power can beused, it can be important to provide the greatest possible production ofhalogenated mixed oxidants or mixed-oxidant agents for each watt ofpower consumed. This ensures long battery life, greater consumerconvenience, smaller and more efficient electrochemical cells, andgreater consumer value.

[0051] The productivity of an electrochemical cell can be expressed byequation (I),

η=(CCI)(Q)/(I)(V)  (I)

[0052] wherein:

[0053] η units are micrograms of chlorine per minute, per watt of powerused;

[0054] CCI can be the concentration of the generated chlorineequivalent, as determined by the DPD Method, in milligrams per liter(mg/l);

[0055] I can be the electric current in amps;

[0056] Q can be the volumetric flow rate in milliliters per minute(ml/m); and

[0057] V can be electric potential across the electrochemical cell involts.

[0058] The productivity η of the electroytic device used in accordancewith the present invention can be typically greater than 100, and moretypically greater than 250. In preferred embodiments of theelectrochemical cell, the productivity η can be more than about 500, andmore preferably more than about 1000, when the aqueous electrolyticsolution has a concentration of halogen ions of more than 0.001% (10ppm) and less than 0.1%. Preferably, the cell and/or device has theabove-described efficiencies when the electric current can be betweenabout 100 milliamps and about 2000 milliamps, with typical currentdensities of between about 5 milliamps/cm² and 100 milliamps/cm² ofexposed anode electrode surface, and more preferably between about 10milliamps and 50 milliamps/cm². Since the electrical potentials requiredto convert chloride to chlorine can be about 1.36V, a voltage potentialgreater than 1.36V across the passage will generate a proportionallygreater amount of halogenated mixed oxidants from the chloride ions.

[0059] The voltage potential maintained between any pair of anode andcathode electrodes should be generally greater than 1.36V, and generallyless than about 12 volts, and can be preferably between about 2.0V and6V, and more preferably between about 3V and 4.5V. For self-poweredself-contained devices, batteries are the preferred electrical currentsources. To achieve the extended life from a set of batteries, celland/or device can be preferably designed to draw a total power of 20watts or less, preferably 5 watts or less, more preferably 2.5 watts orless, and most preferably I watt or less, across the electrode pairs ofthe electrochemical cell.

[0060] Generally, the electrochemical cell has a cell gap spacinggreater than about 0.05 mm, preferably greater than 0.10 mm, morepreferably greater than 0.15 mm, and most preferably greater than about0.20 mm, and a cell gap spacing less than about 5 mm, preferably lessthan about 2.0 mm, more preferably less than about 0.80 mm, and mostpreferably less than about 0.50 mm. The more preferable cell gapspacings are for use with electrolytic solutions that contain aconcentration of halide ions of less than about 200 ppm, and a specificconductivity p of greater than about 250 μS/cm.

[0061] The residence time between the inlet and outlet of the anode andcathode pair can be generally less than 10 seconds and preferably can beless than 5 seconds, in more preferred embodiments, between about 0.01seconds and about 1.5 seconds, and most preferably between 0.05 andabout 0.5 seconds. The residence time can be approximated by dividingthe total volume of the passage between the anode and cathode pair bythe average flow rate of water through the electrochemical cell.

[0062] Operation and effectiveness of the cell and/or device requiresthat the aqueous electrolytic solution passes through theelectrochemical cell in a quantity sufficient to generate an effectiveproduction of the halogenated mixed oxidants for the intended purpose.In general, without some means of moving the aqueous electrolyticsolution through the electrochemical cell, as opposed to just fillingthe electrochemical cell, low levels of the halogenated mixed oxidantswill be produced. Electrolytic solution comprising wash and/or rinseliquor can be moved through the cell and/or device by pumping throughthe electrochemical cell via an internal and/or external pumping means.Alternatively, cell and/or device can be placed into an area of theappliance washing basin where there can be water flow sufficient to passthrough the electrochemical cell by gravity flow.

[0063] The following U.S. Patents disclose electrochemical cells: U.S.Pat. No. 5,932,171; U.S. Pat. No. 4,481,086; U.S. Pat. No. 4,434,629;U.S. Pat. No. 4,493,760; U.S. Pat. No. 4,402,197; U.S. Pat. No.5,250,160; U.S. Pat. No. 5,534,120; U.S. Pat. No. 5,947,135; JPApplication No. 10057297A; JP Application No. 10179489A; JP ApplicationNo. 10033448A; JP Patent No. 09122060; JP Patent No. 2000116587; JPPatent No. 10178491; and EP Application No. 0983806A1.

[0064] Composition

[0065] Electrolyzed water when combined with a specific ADD composition,such as a phosphate and/or silicate in the presence of a halogenatedsalt, can be particularly effective in removing a wide range of soils,microorganisms, and/or stains from soiled tableware.

[0066] (a) Halogenated Salt

[0067] The present invention can comprise one or more halogenated saltsselected from the group consisting of halite salt, halide salt, andmixtures thereof. The level of halogenated salt comprised in the washand/or rinse liquor can be selected based on the required bleaching ordisinfection required by the halogenated mixed oxidants, in addition tothe conversion efficiency of the clectrochemical cell to convert thehalogenated salt to the halogenated mixed oxidants. The level ofhalogenated salt can be generally from about 1 ppm to about 10,000 ppm.For disinfection of wash and/or rinse liquor, a halogenated salt levelcan be preferably from about 1 ppm to about 5000 ppm, and morepreferably about 10 ppm to about 1000 ppm. The resulting halogenatedmixed-oxidant level can be from about 0.1 ppm to about 10,000 ppm,preferably from about 1 ppm to about 200 ppm. For bleaching purposes, ahalogenated salt level of from about 100 ppm to about 10,000 ppm can bepreferred.

[0068] The range of halogenated mixed oxidants conversion that can beachievable in the electrochemical cells of the present inventiongenerally ranges from less than about 1% to about 99%. The level ofconversion can be dependent most significantly on the design of theelectrochemical cell, herein described, as well as on the electricalcurrent properties used in the electrochemical cell.

[0069] In certain circumstances, halogenated salts of calcium andmagnesium having a reduced solubility in water, as compared to sodiumhalogenated salts, control the rate of dissolution of the halogenatedsalt. The ADD composition can also be formulated with other organic andinorganic materials to control the rate of dissolution of thehalogenated salt. Preferred can be a slow dissolving salt particleand/or tablet, to release sufficient halogenated salt to form aneffective amount of halogenated precursor product. The release amount ofthe halogenated salt can be typically, between 1 milligram to 10 gramshalogenated salt, for each liter of solution passed through theelectrochemical cell. The ADD composition can comprise a simpleadmixture of the halogenated salt with the dissolution controlmaterials, which can be selected from various well-known encapsulatingmaterials, including but not limited to fatty alcohol, fatty acids, andwaxes.

[0070] The ADD composition of the present invention can comprise a localsource of halogenated salt, and a means for delivering the halogenatedsalt to the wash and/or rinse liquor. This embodiment can beadvantageously used in those situations when the target water to betreated with the electrochemical cell does not contain a sufficientamount, or any, of the halogenated salt. The local source of halogenatedsalt can be released into a stream of the aqueous solution, which thenultimately passes through the electrochemical cell. The local source ofhalogenated salt can also be released into at least some of the washand/or rinse liquor present in the washing basin of the automaticdishwashing appliance, which portion can be then drawn into theelectrochemical cell. Preferably, in order to maximize the conversion tohalogenated mixed oxidants, and limit the addition of salts to the washand/or rinse liquor, generally all the local source of halogenated saltpasses through the electrochemical cell. The local source of halogenatedsalt can also supplement any residual levels of halogenated salt alreadycontained in incoming tap water and/or the wash and/or rinse liquor.

[0071] The local source of halogen ions can be from an ADD compositionand/or rinse aid composition, a concentrated brine solution, ahalogenated salt tablet, granule, or pellet in fluid contact with theaqueous electrolytic solution, or in a a porous basket hanging on therack of the automatic dishwashing appliance, or both. A preferredlocalized source of halogen ions can be a solid form, such as a pill ortablet, of halide salt, such as sodium chloride (common salt) or sodiumchlorite. The means for delivering the local source of halogen ions cancomprise a salt chamber or a porous basket comprising the halogenatedsalt, preferably a pill of tablet, through which at least some of theaqueous electrolytic solution will pass, thereby dissolving at leastsome of the halide salt into the portion of water. The salted portion ofwater then ultimately passes into the electrochemical cell. The saltchamber or a porous basket can comprise a salt void that can be formedin the body and positioned in fluid communication with the portion ofwater that will pass through the electrochemical cell.

[0072] One embodiment of the present invention relates to an ADDcomposition, wherein the halogenated salt can be in a form selected fromthe group characterized by low water solubility, contained within amedium for controlled release, and combinations thereof.

[0073] Another embodiment of the present invention relates to an ADDcomposition, wherein the controlled release form provides a local sourceof the halogenated salt comprising a form such that once placed inside adishwashing appliance it provides a controlled release of steady levelsof halogen dioxide salts into the wash and/or rinse liquors duringoperation of an automatic dishwasher over a period of from 1 day to 365days of regular household and/or commercial use.

[0074] (i) Halogen Dioxide Salt—The precursor material from whichhalogen dioxide can be formed can be referred to as a halogen dioxidesalt. The halogen dioxide salt of the present invention having theformula (M)_(x)(XO₂)_(y), wherein X can be Cl, Br, or I and wherein Mcan be a metal ion or cationic entity, and wherein x and y are chosensuch that the salt can be charge balanced. The halogen dioxide salt cancomprise two or more salts in various mixtures.

[0075] The most preferred halite salt can be sodium chlorite. Sodiumchlorite can be not a salt ordinarily found in tap water, well water,and other water sources. Consequently, an amount of the sodium chloritesalt can be added into the wash and/or rinse liquor at a desiredconcentration generally of at least about 0.1 ppm.

[0076] The wash and/or rinse liquor can comprise substantially nochloride (Cl⁻) or other halide ions, which upon electrolysis can form amixed oxidant, including hypochlorite. Preferably, electrolyzeddischarge effluent can comprise less than about 1.0 ppm, and morepreferably less than 0.1 ppm, of chlorine. The wash and/or rinse liquorcomprising the sodium chlorite can be provided in a variety of ways.

[0077] One embodiment of the present invention relates to an ADDcomposition comprising sodium chlorite, preferably, a concentratedsolution about 2% to about 35% sodium chlorite by weight of thecomposition in the form of a liquid, liquitab, and/or gel.

[0078] One embodiment of the present invention relates to an automaticdishwashing composition for treating tableware in an automaticdishwashing appliance comprising an electrochemical cell and/orelectrolytic device for improved tableware cleaning, sanitizing, and/orstain removal, the composition comprising: (a) a halogen dioxide salthaving the formula (M)_(x)(XO₂)_(y), wherein X can be Cl, Br, or I andwherein M can be a metal ion or cationic entity, and wherein x and y arechosen such that the salt can be charge balanced; and (b) a componentselected from the group consisting of a builder, suds suppressor,perfume, enzyme, bleach-scavenging agent, a metal-protecting agent, andmixtures thereof; wherein the composition can be optionally free ofbleach.

[0079] Another embodiment of the present invention relates to an ADDcomposition, wherein the halogenated salt can comprise a salt selectedfrom the group consisting of NaClO₂, KClO₂, and mixtures thereof.Another embodiment of the present invention relates to an ADDcomposition, wherein NaClO₂, KClO₂, and mixtures thereof, can be presentat a level of greater than about 0.1%, preferably at a level greaterthan about 0.5%, more preferably at a level of greater than about 1.0%by weight of the composition, and most preferably at a level of greaterthan about 2%, by weight of the composition.

[0080] (ii) Other Halogenated Salts—In substitution of and/or additionto halogen dioxide salt, the present invention can comprise one or morehalide salts. The halide salt of the present invention having theformula (M)_(x)(X)_(y) wherein X can be Cl, Br, or I and wherein M canbe a metal ion or cationic entity, and wherein x and y are chosen suchthat the salt can be charge balanced, can be used to enhance thedisinfection and bleaching performance of the effluent that can bedischarged from the electrochemical cell, or to provide otherhalogenated mixed oxidants, when preferred, in response to the passingof electrical current through the electrochemical cell.

[0081] One embodiment of the present invention relates to an automaticdishwashing composition for treating tableware in an automaticdishwashing appliance comprising an electrochemical cell and/orelectrolytic device for improved tableware cleaning, sanitizing, and/orstain removal, the composition comprising: (a) at least about 0.1%, byweight of the composition, of a halogenated salt having the formula(M)_(x)(X)_(y), wherein X can be Cl, Br, or I and wherein M can be ametal ion or cationic entity, and wherein x and y are chosen such thatthe salt can be charge balanced; and (b) a component selected from thegroup consisting of a builder, suds suppressor, perfume, enzyme,bleach-scavenging agent, a metal-protecting agent, enzymes, and mixturesthereof; wherein the composition can be optionally free of bleach.

[0082] Another embodiment of the present invention relates to an ADDcomposition comprising NaCl, KCl, and mixtures thereof, at a level ofgreater than about 0.1%, preferably at a level greater than about 0.5%by weight of the composition, more preferably at a level of greater thanabout 1% by weight of the composition. most preferably at a level ofgreater than about 2%, by weight of the composition.

[0083] (b) Builders

[0084] Detergent builders are included in the compositions herein toassist in controlling mineral hardness and dispersancy. Inorganic aswell as organic builders can be used. Builders are typically used inautomatic dishwashing, for example to assist in the removal ofparticulate soils. The level of builder can vary widely depending uponthe end use of the composition and its desired physical form. Whenpresent, the compositions will typically comprise at least about 1%builder. Liquid formulations typically comprise from about 5% to about50%, more typically about 5% to about 30%, by weight, of detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

[0085] One embodiment of the present invention relates to an ADDcomposition, wherein the builder can be selected from the groupconsisting of phosphate, phosphate oligomers or polymers and saltsthereof, silicate oligomers or polymers and salts thereof,aluminosilicates, magnesioaluminosiliates, citrate, and mixturesthereof.

[0086] (i) Phosphate Builders—Phosphate detergent builders for use inADD compositions are well known. They include, but are not limited to,the alkali metal, ammonium and alkanolammonium salts of polyphosphates(exemplified by the tripolyphosphates, pyrophosphates, and glassypolymeric meta-phosphates). Phosphate builder sources are described indetail in Kirk Othmer, 3rd Edition, Vol. 17, pp. 426-472 and in“Advanced Inorganic Chemistry” by Cotton and Wilkinson, pp. 394-400(John Wiley and Sons, Inc.; 1972).

[0087] Inorganic or non-phosphate P-containing detergent buildersinclude, but are not limited to, phosphonates, phytic acid, silicates,carbonates (including bicarbonates and sesquicarbonates), sulfates,citrate, zeolite or layered silicate, and aluminosilicates. See U.S.Pat. No. 4,605,509 for examples of preferred aluminosilicates.

[0088] (ii) Silicate Builders—The present automatic dishwashingdetergent compositions can further comprise water-soluble silicates.Water-soluble silicates herein are any silicates which are soluble tothe extent that they do not adversely affect spotting/filmingcharacteristics of the ADD composition.

[0089] Examples of silicates are sodium metasilicate and, moregenerally, the alkali metal silicates, particularly those having aSiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1; and layered silicates, suchas the layered sodium silicates described in U.S. Pat. No. 4,664,839,issued can 12, 1987 to H. P. Rieck. NaSKS-6® can be a crystallinelayered silicate marketed by Hoechst (commonly abbreviated herein as“SKS-6”). Unlike zeolite builders, Na SKS-6 and other water-solublesilicates useful herein do not contain aluminum. NaSKS-6 can be the6-Na₂SiO₅ form of layered silicate and can be prepared by methods suchas those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6can be a preferred layered silicate for use herein, but other suchlayered silicates, such as those having the general formulaNaMSi_(x)O_(2x+1).yH₂O wherein M can be sodium or hydrogen, x can be anumber from 1.9 to 4, preferably 2, and y can be a number from 0 to 20,preferably 0 can be used. Various other layered silicates from Hoechstinclude NaSKS-5, NaSKS-7 and NaSKS-11, as the α-, β- and γ-forms. Othersilicates can also be useful, such as for example magnesium silicate,which can serve as a crispening agent in granular formulations, as astabilizing agent for oxygen bleaches, and as a component of sudscontrol systems.

[0090] Silicates particularly useful in automatic dishwashing (ADD)applications include granular hydrous 2-ratio silicates such asBRITESIL® H20 from PQ Corp., and the commonly sourced BRITESIL® H24though liquid grades of various silicates can be used when the ADDcomposition has liquid form. Within safe limits, sodium metasilicate orsodium hydroxide alone or in combination with other silicates can beused in an ADD context to boost wash pH to a desired level.

[0091] Aluminosilicate builders can be used in the present compositionsthough are not preferred for automatic dishwashing detergents.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:Na₂O.Al₂O₃.xSiOz.yH₂O wherein z and y are integers of at least about 6,the molar ratio of z to y can be in the range from 1.0 to about 0.5, andx can be an integer from about 15 to about 264.

[0092] Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials can be disclosed in U.S. Pat. No. 3,985,669, Krummel,et al, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inanother embodiment, the crystalline aluminosilicate ion exchangematerial has the formula: Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O wherein x can befrom about 20 to about 30, especially about 27. This material can beknown as Zeolite A. Dehydrated zeolites (x=0-10) can also be usedherein. Preferably, the aluminosilicate has a particle size of about0.1-10 microns in diameter. Individual particles can desirably be evensmaller than 0.1 micron to further assist kinetics of exchange throughmaximization of surface area. High surface area also increases utilityof aluminosilicates as adsorbents for surfactants, especially ingranular compositions. Aggregates of silicate or aluminosilicateparticles can be useful, a single aggregate having dimensions tailoredto minimize segregation in granular compositions, while the aggregateparticle remains dispersible to submicron individual particles duringthe wash. As with other builders such as carbonates, it can be desirableto use zeolites in any physical or morphological form adapted to promotesurfactant carrier function, and appropriate particle sizes can befreely selected by the formulator.

[0093] (iii) Carbonate Builders—Examples of carbonate builders are thealkaline earth and alkali metal carbonates as disclosed in German PatentApplication No. 2,321,001 published on Nov. 15, 1973. Various grades andtypes of sodium carbonate and sodium sesquicarbonate can be used,certain of which are particularly useful as carriers for otheringredients, especially detersive surfactants.

[0094] (iv) Organic Detergent Builders—Organic detergent builderssuitable for the purposes of the present invention include, but are notrestricted to, a wide variety of polycarboxylate compounds. As usedherein, “polycarboxylate” refers to compounds having a plurality ofcarboxylate groups, preferably at least about 3 carboxylates.Polycarboxylate builder can generally be added to the composition inacid form, but can also be added in the form of a neutralized salt or“overbased”. When utilized in salt form, alkali metals, such as sodium,potassium, and lithium, or alkanolammonium salts are preferred.

[0095] Included among the polycarboxylate builders are a variety ofcategories of useful materials. One important category ofpolycarboxylate builders encompasses the ether polycarboxylates,including oxydisuccinate, as disclosed in Berg, U.S. Pat. No. 3,128,287,issued Apr. 7, 1964, and Lamberti et al, U.S. Pat. No. 3,635,830, issuedJan. 18, 1972. See also “TMS/TDS” builders of U.S. Pat. No. 4,663,071,issued to Bush et al, on can 5, 1987. Suitable ether polycarboxylatesalso include cyclic compounds, particularly alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

[0096] (v) Other Useful Builders—Other useful detergency buildersinclude the ether hydroxypolycarboxylates, copolymers of maleicanhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, thevarious alkali metal, ammonium and substituted ammonium salts ofpolyacetic acids such as ethylenediaminetetraacetic acid andnitrilotriacetic acid, as well as polycarboxylates such as melliticacid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and solublesalts thereof.

[0097] Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty laundry detergent and automatic dishwashingformulations due to their availability from renewable resources andtheir biodegradability. Citrates can also be used in combination withzeolite, the aforementioned BRITESIL types, and/or layered silicatebuilders. Oxydisuccinates are also useful in such compositions andcombinations.

[0098] Also suitable in the detergent compositions of the presentinvention are the 3,3-dicarboxy-4-oxa-1,6-hexanedionates and the relatedcompounds disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28,1986. Useful succinic acid builders include the C₅-C₂₀ alkyl and alkenylsuccinic acids and salts thereof. A particularly preferred compound ofthis type can be dodecenylsuccinic acid. Specific examples of succinatebuilders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

[0099] Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also U.S. Pat. No. 3,723,322.

[0100] Where phosphorus-based builders can be used, the various alkalimetal phosphates such as the well-known sodium tripolyphosphates, sodiumpyrophosphate and sodium orthophosphate can be used. Phosphonatebuilders such as ethane-1-hydroxy-1,1-diphosphonate and other knownphosphonates (see, for example, U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,400,148 and 3,422,137) can also be used though suchmaterials are more commonly used in a low-level mode as chelants orstabilizers.

[0101] Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforethe builders, especially citrate and/or the succinate builders, toprovide additional builder activity but are generally not desired. Suchuse of fatty acids will generally result in a diminution of sudsing inlaundry compositions, which can need to be taken into account by theformulator. Fatty acids or their salts are undesirable in AutomaticDishwashing (ADD) embodiments in situations wherein soap scums can formand be deposited on dishware.

[0102] (c) Suds Suppressor

[0103] The ADD compositions of the present invention can optionallycontain an alkyl phosphate ester suds suppressor, a silicone sudssuppressor, or combinations thereof. Levels in general are from 0% toabout 10%, preferably, from about 0.001% to about 5%. However, generally(for cost and/or deposition considerations) preferred compositionsherein do not comprise suds suppressors or comprise suds suppressorsonly at low levels, e.g., less than about 0.1% of active sudssuppressing agent.

[0104] Silicone suds suppressor technology and other defoaming agentsuseful herein are extensively documented in “Defoaming, Theory andIndustrial Applications”, Ed., P. R. Garrett, Marcel Dekker, N.Y., 1973,ISBN 0-8247-8770-6, incorporated herein by reference. See especially thechapters entitled “Foam control in Detergent Products” (Ferch et al) and“Surfactant Antifoams” (Blease et al). See also U.S. Pat. Nos. 3,933,672and 4,136,045. Highly preferred silicone suds suppressors are thecompounded types known for use in laundry detergents such as heavy-dutygranules, although types hitherto used only in heavy-duty liquiddetergents can also be incorporated in the instant compositions. Forexample, polydimethylsiloxanes having trimethylsilyl or alternateendblocking units can be used as the silicone. These can be compoundedwith silica and/or with surface-active non-silicon components, asillustrated by a suds suppressor comprising 12% silicone/silica, 18%stearyl alcohol and 70% starch in granular form. A suitable commercialsource of the silicone active compounds can be Dow Corning Corp.

[0105] If it can be desired to use a phosphate ester, suitable compoundsare disclosed in U.S. Pat. No. 3,314,891, issued Apr. 18, 1967, toSchmolka et al, incorporated herein by reference. Preferred alkylphosphate esters contain from 16-20 carbon atoms. Highly preferred alkylphosphate esters are monostearyl acid phosphate or monooleyl acidphosphate, or salts thereof, particularly alkali metal salts, ormixtures thereof.

[0106] It has been found preferable to avoid the use of simplecalcium-precipitating soaps as antifoams in the present compositions asthey tend to deposit on the dishware. Indeed, phosphate esters are notentirely free of such problems and the formulator will generally chooseto minimize the content of potentially depositing antifoams in theinstant compositions.

[0107] One embodiment of the present invention relates to an ADDcomposition, wherein the suds suppressor can be selected from the groupconsisting of low-foaming nonionic surfactants, low-foaming nonionicsurfactants with a cloud point below about 30° C., alkoxylates or mixedalkoxylates of linear fatty alcohols, alkoxylates or mixed alkoxylatesof alkylphenols, block co-polymers of ethylene and propylene glycol,_(9/11)EO₈-cyclohexyl acetal alkyl capped nonionic, C₁₁EO₇-n-butylacetal, C_(9/11)EO₈-2-ethylhexyl acetal, C₁₁EO₈-pyranyl, alcoholalkoxylate, and mixtures thereof.

[0108] (d) Perfume

[0109] (i) Non-Blooming Perfumes—Perfumes and perfumery ingredientsuseful in the present compositions and processes comprise a wide varietyof natural and synthetic chemical ingredients, including, but notlimited to, aldehydes, ketones, esters, and the like. Also included arevarious natural extracts and essences which can comprise complexmixtures of ingredients, such as orange oil, lemon oil, rose extract,lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil,cedar, and the like. Finished perfumes can comprise extremely complexmixtures of such ingredients. Finished perfumes typically comprise fromabout 0.01% to about 2%, by weight, of the detergent compositionsherein, and individual perfumery ingredients can comprise from about0.0001% to about 90% of a finished perfume composition.

[0110] Non-limiting examples of perfume ingredients useful hereininclude: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone;methyl dihydrojasmonate; methyl1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone;7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

[0111] Particularly preferred perfume materials are those that providethe largest odor improvements in finished product compositionscontaining cellulases. These perfumes include but are not limited to:hexyl cinnamic aldehyde;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

[0112] Other perfume materials include essential oils, resinoids, andresins from a variety of sources including, but not limited to: Perubalsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil,benzoin resin, coriander and lavandin. Still other perfume chemicalsinclude phenyl ethyl alcohol, terpineol, linalool, linalyl acetate,geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzylacetate, and eugenol. Carriers such as diethylphthalate can be used inthe finished perfume compositions.

[0113] (ii) Blooming Perfumes—Blooming perfume compositions, asdisclosed herein, can be formulated into automatic dishwashing detergentcompositions and provide significantly better noticeability to theconsumer than non-blooming perfume compositions not containing asubstantial amount of blooming perfume ingredients. Additionally,residual perfume can be not desirable on many surfaces, includingdishes, glasses and cutlery, especially those made of plastic, rubberand silicone.

[0114] A blooming perfume ingredient can be characterized by its boilingpoint (B.P.) and its octanol/water partition coefficient (P). Theoctanol/water partition coefficient of a perfume ingredient can be theratio between its equilibrium concentrations in octanol and in water.The preferred perfume ingredients of this invention have a B.P.,determined at the normal, standard pressure of about 760 mm Hg, of about260° C. or lower, preferably less than about 255° C.; and morepreferably less than about 250° C., and an octanol/water partitioncoefficent P of about 1,000 or higher. Since the partition coefficientsof the preferred perfume ingredients of this invention have high values,they are more conveniently given in the form of their logarithm to thebase 10, logP. Thus the preferred perfume ingredients of this inventionhave logP at □□□ C of about 3 or higher.

[0115] One embodiment of the present invention relates to an ADDcomposition, wherein the perfume can be from about 0.01% to about 5%, byweight, a blooming perfume composition, wherein the blooming perfumecomposition can comprise from about 50% to about 99% of blooming perfumeingredients having a boiling point of less than about 260° C. and aClogP of at least about 3, and wherein the blooming perfume compositioncomprising at least about 5 different blooming perfume ingredients, andfrom about 0.5% to about 10% of base masking perfume ingredients havinga boiling point of more than about 260° C. and a ClogP of at least about3.

[0116] The following U.S. Patents disclose perfumes: U.S. Pat. No.6,143,707; U.S. Pat. No. 6,228,821; U.S. Pat. No. 5,929,022; and U.S.Pat. No. 5,670,466.

[0117] (e) Bleach-Scavenging Agent

[0118] Additionally, from 0% to about 10%, preferably from about 0.01%to about 6% by weight, of bleach-scavengers can be added to compositionsof the present invention to prevent chlorine and/or oxygen bleachspecies present in the wash and/or rinse liquor from attacking andinactivating the enzymes, especially under alkaline washing conditions.While chlorine levels in tap water can be small, typically in the rangefrom about 0.5 ppm to about 1.75 ppm, the available chlorine in thetotal volume of water that comes in contact with the enzyme duringdishwashing can be usually large; accordingly, enzyme stability in-usecan be problematic.

[0119] Suitable bleach-scavenger anions are salts containing ammoniumcations. These can be selected from the group consisting of reducingmaterials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide,etc., antioxidants like carbonate, ascorbate, etc., organic amines suchas ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereofand monoethanolamine (MEA), and mixtures thereof. Other conventionalscavenging anions like sulfate, bisulfate, carbonate, bicarbonate,percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate,sodium perborate monohydrate, percarbonate, phosphate, condensedphosphate, acetate, benzoate, citrate, formate, lactate, malate,tartrate, salicylate, etc. and mixtures thereof can also be used.

[0120] One embodiment of the present invention relates to ableach-scavenging agent selected from the group consisting of perborate,percarbonate, ascorbic acid or derivatives thereof, carbamate, ammonium,sulfite, bisulfite, aluminum tristearate, sodium silicate,benzotriazole, amines, amino acids, and mixtures thereof. Anotherembodiment of the present invention relates to an ADD composition thatdoes not contain chlorine bleach, oxygen bleach, and mixtures thereof.

[0121] (f) Metal-Protecting Agent

[0122] The present ADD compositions can contain one or more materialcare agents which are effective as corrosion inhibitors and/oranti-tarnish aids. Such materials are preferred components of machinedishwashing compositions especially in certain European countries wherethe use of electroplated nickel silver and sterling silver can be stillcomparatively common in domestic flatware, or when aluminium protectioncan be a concern and the composition can be low in silicate. Generally,such material care agents include metasilicate, silicate, bismuth salts,manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans,aluminium fatty acid salts, and mixtures thereof.

[0123] When present, such protecting materials are preferablyincorporated at low levels, e.g., from about 0.01% to about 5% of theADD composition. Suitable corrosion inhibitors include paraffin oil,typically a predominantly branched aliphatic hydrocarbon having a numberof carbon atoms in the range of from about 20 to about 50; preferredparaffin oil can be selected from predominantly branched C₂₅₋₄₅ specieswith a ratio of cyclic to noncyclic hydrocarbons of about 32:68. Aparaffin oil meeting those characteristics can be sold by Wintershall,Salzbergen, Germany, under the trade name WINOG 70. Additionally, theaddition of low levels of bismuth nitrate (i.e., Bi(NO₃)₃) can be alsopreferred.

[0124] Other corrosion inhibitor compounds include benzotriazole andcomparable compounds; mercaptans or thiols including thionaphtol andthioanthranol; and finely divided Aluminium fatty acid salts, such asaluminium tristearate. The formulator will recognize that such materialswill generally be used judiciously and in limited quantities so as toavoid any tendency to produce spots or films on glassware or tocompromise the bleaching action of the compositions. For this reason,mercaptan anti-tarnishes which are quite strongly bleach-reactive andcommon fatty carboxylic acids which precipitate with calcium inparticular are preferably avoided.

[0125] One embodiment of the present invention relates to ametal-protecting agent selected from the group consisting of perborate,percarbonate, ascorbic acid or derivatives thereof, carbamate, ammonium,sulfite, bisulfite, aluminum tristearate, sodium silicate,benzotriazole, amines, amino acids, and mixtures thereof.

[0126] Adjunct Ingredients

[0127] Detersive ingredients or adjuncts optionally included in theinstant ADD compositions can include one or more materials for assistingor enhancing cleaning, sanitizing and stain removal performance oftableware treated by electrolyzed water in an automatic dishwashingappliance containing an electrochemical cell and/or electrolytic device.They are further selected based on the form of the composition, i.e.,whether the composition can be to be sold as a liquid, paste(semi-solid), or solid form (including tablets and the preferredgranular forms for the present compositions).

[0128] Adjuncts which can also be included in compositions of thepresent invention, at their conventional art-established levels for use(generally, adjunct materials comprise, in total, from about 1% to about90%, preferably from about 5% to about 75%, more preferably from about10% to about 50%, by weight of the compositions), and can include otheractive ingredients such as nanoparticles, functionalized surfacemolecules, polymers, surfactants, co-surfactants, metal ions, proteins,dyes, acids, bases, organic solvents, enzymes, enzyme stabilizingsystems, chelants, optical brighteners, soil release agents, wettingagents, dispersants, blooming perfumes, colorants, filler salts,hydrotropes, perservatives, anti-oxidants, germicides, fungicides, colorspeckles, silvercare, anti-tarnishing agents, alkalinity sources,solubilizing agents, carriers, electrode maintenance and/or descalingagents, processing aids, pigments, and pH control agents, bleachingagent, bleach activators, bleach catalysts and mixtures thereof. Theseadjuncts are described in detail in U.S. Pat. No. 6,143,707, Trinh etal., incorporated herein by reference.

[0129] The precise nature of these additional detergent ingredients, andlevels of incorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which the compositioncan be to be used. The selection of the adjunct will depend upon thetype and use of the composition. Non-limiting illustrative examples ofcompositions as well as suitable adjunct(s) for the illustrativecompositions are described hereinafter. Particularly preferred adjunctsare surfactants, enzymes, chelants, dispersant polymers, thickeners, andpH adjusting agents as described in detail hereinafter.

[0130] (a) Surfactant

[0131] One embodiment of the present invention relates to an ADDcomposition comprising a surfactant can be selected from the groupconsisting of anionic surfactants, cationic surfactants, nonionicsurfactants, amphoteric surfactants, ampholytic surfactants,zwitterionic surfactants, and mixtures thereof.

[0132] It should be noted that low foaming nonionic surfactants areuseful in automatic dishwashing to assist cleaning, help defoam foodsoil foams, especially from proteins, and to help controlspotting/filming and are desirably included in the present detergentcompositions at levels of from about 0.1% to about 20%, preferably fromabout 0.5% to about 5%, by weight of the composition. In general,bleach-stable surfactants are preferred. ADD compositions of the presentinvention preferably comprise low foaming nonionic surfactants (LFNIs).

[0133] LFNIs are most typically used in ADDs on account of the improvedwater-sheeting action (especially from glass) which they confer to theADD composition. They also encompass non-silicone, nonphosphatepolymeric materials further illustrated hereinafter which are known todefoam food soils encountered in automatic dishwashing.

[0134] Preferred LFNIs include nonionic alkoxylated surfactants,especially ethoxylates derived from primary alcohols, and blends thereofwith more sophisticated surfactants, such as thepolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. The PO/EO/PO polymer-type surfactants are well-known tohave foam suppressing or defoaming action, especially in relation tocommon food soil ingredients such as egg.

[0135] In a preferred embodiment, the LFNI can be an ethoxylatedsurfactant derived from the reaction of a monohydroxy alcohol oralkylphenol containing from about 8 to about 20 carbon atoms, with fromabout 6 to about 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis.

[0136] A particularly preferred LFNI can be derived from a straightchain fatty alcohol containing from about 16 to about 20 carbon atoms(C₁₆-C₂₀ alcohol), preferably a C₁₈ alcohol, condensed with an averageof from about 6 to about 15 moles, preferably from about 7 to about 12moles, and most preferably from about 7 to about 9 moles of ethyleneoxide per mole of alcohol. Preferably the ethoxylated nonionicsurfactant so derived has a narrow ethoxylate distribution relative tothe average.

[0137] The LFNI can optionally contain propylene oxide in an amount upto about 15% by weight. Other preferred LFNI surfactants can be preparedby the processes described in U.S. Pat. No. 4,223,163, issued Sep. 16,1980, Builloty, incorporated herein by reference.

[0138] Highly preferred ADDs herein wherein the LFNI can be present makeuse of ethoxylated monohydroxy alcohol or alkyl phenol and additionallycomprise a polyoxyethylene, polyoxypropylene block polymeric compound;the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNIcomprising from about 20% to about 100%, preferably from about 30% toabout 70%, of the total LFNI.

[0139] Suitable block polyoxyethylene-polyoxypropylene polymericcompounds that meet the requirements described hereinbefore includethose based on ethylene glycol, propylene glycol, glycerol,trimethylolpropane and ethylenediamine as initiator reactive hydrogencompound. Polymeric compounds made from a sequential ethoxylation andpropoxylation of initiator compounds with a single reactive hydrogenatom, such as C₁₂₋₁₈ aliphatic alcohols, do not generally providesatisfactory suds control in the instant ADDs. Certain of the blockpolymer surfactant compounds designated PLURONIC® and TETRONIC® by theBASF-Wyandotte Corp., Wyandotte, Mich., are suitable in ADD compositionsof the invention.

[0140] A particularly preferred LFNI contains from about 40% to about70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymerblend comprising about 75%, by weight of the blend, of a reverse blockco-polymer of polyoxyethylene and polyoxypropylene containing 17 molesof ethylene oxide and 44 moles of propylene oxide; and about 25%, byweight of the blend, of a block co-polymer of polyoxyethylene andpolyoxypropylene initiated with trimethylolpropane and containing 99moles of propylene oxide and 24 moles of ethylene oxide per mole oftrimethylolpropane.

[0141] Suitable for use as LFNI in the ADD compositions are those LFNIhaving relatively low cloud points and high hydrophilic-lipophilicbalance (HLB). Cloud points of 1% solutions in water are typically belowabout 32° C. and preferably lower, e.g., 0° C., for optimum control ofsudsing throughout a full range of water temperatures.

[0142] LFNIs which can also be used include a C₁₈ alcoholpolyethoxylate, having a degree of ethoxylation of about 8, commerciallyavailable as SLF18 from Olin Corp., and any biodegradable LFNI havingthe melting point properties discussed hereinabove.

[0143] (b) Co-Surfactant

[0144] The composition of the present invention can further containoptional co-surfactants. These optional surfactants will be preferablybleach stable. Preferred optional co-surfactants are low cloud pointnonionic surfactants, high cloud point nonionic surfactants, anionicsurfactants and mixtures thereof.

[0145] Nonionic co-surfactants useful in the present invention AutomaticDishwashing compositions are when present desirably included in thepresent detergent compositions at levels of from about 0.1% to about 15%of the composition. In general, bleach-stable co-surfactants arepreferred. Nonionic surfactants generally are well known, beingdescribed in more detail in Kirk Othmer's Encyclopedia of ChemicalTechnology, 3rd Ed., Vol. 22, pp. 360-379, “Surfactants and DetersiveSystems”.

[0146] “Cloud point”, as used herein, can be a well known property ofnonionic surfactants which can be the result of the surfactant becomingless soluble with increasing temperature, the temperature at which theappearance of a second phase can be observable can be referred to as the“cloud point” (See Kirk Othmer, pp. 360-362, hereinbefore).

[0147] As used herein, a “low cloud point nonionic co-surfactant” can bedefined as a nonionic surfactant system ingredient having a cloud pointof less than 30□C, preferably less than about 20□C, and most preferablyless than about 10□C. Typical low cloud point nonionic co-surfactantsinclude nonionic alkoxylated surfactants, especially ethoxylates derivedfrom primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic co-surfactantsinclude, for example, ethoxylated-propoxylated alcohol (e.g., OlinCorporation's Poly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated)alcohols (e.g., Olin Corporation's Poly-Tergent® SLF 18B series ofnonionics, as described, for example, in WO 94/22800, published Oct. 13,1994 by Olin Corporation).

[0148] Nonionic co-surfactants can optionally contain propylene oxide inan amount up to about 15% by weight. Other preferred nonionicco-surfactants can be prepared by the processes described in U.S. Pat.No. 4,223,163, issued Sep. 16, 1980, Builloty, incorporated herein byreference.

[0149] Low cloud point nonionic co-surfactants additionally comprise apolyoxyethylene, polyoxypropylene block polymeric compound. Blockpolyoxyethylene-polyoxypropylene polymeric compounds include those basedon ethylene glycol, propylene glycol, glycerol, trimethylolpropane andethylenediamine as initiator reactive hydrogen compound. Certain of theblock polymer surfactant compounds designated PLURONIC®, REVERSEDPLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Mich.,are suitable in ADD compositions of the invention. Preferred examplesinclude REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such co-surfactantsare typically useful herein as low cloud point nonionic surfactants.

[0150] As used herein, a “high cloud point nonionic co-surfactant” canbe defined as a nonionic surfactant system ingredient having a cloudpoint of greater than 40□C, preferably greater than about 50□C, and morepreferably greater than about 60□C. Preferably the nonionicco-surfactant system can comprise an ethoxylated surfactant derived fromthe reaction of a monohydroxy alcohol or alkylphenol containing fromabout 8 to about 20 carbon atoms, with from about 6 to about 15 moles ofethylene oxide per mole of alcohol or alkyl phenol on an average basis.Such high cloud point nonionic co-surfactants include, for example,Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (suppliedby Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

[0151] It can be also preferred for purposes of the present inventionthat the high cloud point nonionic co-surfactant further have ahydrophile-lipophile balance (“HLB”; see Kirk Othmer hereinbefore) valuewithin the range of from about 9 to about 15, preferably 11 to 15. Suchmaterials include, for example, Tergitol 15S9 (supplied by UnionCarbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8(supplied by Shell).

[0152] Another preferred high cloud point nonionic co-surfactant can bederived from a straight or preferably branched chain or secondary fattyalcohol containing from about 6 to about 20 carbon atoms (C₆-C₂₀alcohol), including secondary alcohols and branched chain primaryalcohols. Preferably, high cloud point nonionic co-surfactants arebranched or secondary alcohol ethoxylates, more preferably mixed C9/11or C11/15 branched alcohol ethoxylates, condensed with an average offrom about 6 to about 15 moles, preferably from about 6 to about 12moles, and most preferably from about 6 to about 9 moles of ethyleneoxide per mole of alcohol. Preferably the ethoxylated nonionicco-surfactant so derived has a narrow ethoxylate distribution relativeto the average.

[0153] When the optional co-surfactants are a mixture of low cloud pointnonionics and high cloud point nonionics it can be preferred that themixture can be combined in a weight ratio preferably within the range offrom about 10:1 to about 1:10.

[0154] The anionic co-surfactant can be selected fromalkylethoxycarboxylates, alkylethoxysulfates, with the degree ofethoxylation greater than 3 (preferably 4 to 10; more preferably 6 to8), and chain length in the range of C8 to C16, preferably 11-15.Additionally, branched alkylcarboxylates have been found to be useful inADD compositions when the branch occurs in the middle and the averagetotal chain length can be 10 to 18, preferably 12-16 with the sidebranch 2-4 carbons in length. An example can be 2-butyloctanoic acid.The anionic co-surfactant can be typically of a type having goodsolubility in the presence of calcium. Such anionic co-surfactants arefurther illustrated by alkyl(polyethoxy)sulfates (AES), alkyl(polyethoxy)carboxylates (AEC), and short chained C₆-C₁₀ alkyl sulfatesand sulfonates. Straight chain fatty acids have been shown to beineffective due to their sensitivity to calcium.

[0155] (c) Enzyme

[0156] “Detergent enzyme”, as used herein, means any enzyme having acleaning, stain removing or otherwise beneficial effect in an ADDcomposition. Preferred enzymes are hydrolases such as proteases,amylases and lipases. Highly preferred for automatic dishwashing areamylases and/or proteases, including both current commercially availabletypes and improved types which, though more bleach compatible, have aremaining degree of bleach deactivation susceptibility.

[0157] Enzyme-containing compositions, especially liquid compositions,herein can comprise from about 0.001% to about 10%, preferably fromabout 0.005% to about 8%, most preferably from about 0.01% to about 6%,by weight of an enzyme stabilizing system. The enzyme stabilizing systemcan be any stabilizing system which can be compatible with the detersiveenzyme. Such stabilizing systems can comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acid, boronic acid, andmixtures thereof.

[0158] One embodiment of the present invention relates to a liquid,liquitab, and/or gel automatic dishwashing composition for treatingtableware in an automatic dishwashing appliance comprising anelectrochemical cell for improved tableware cleaning, sanitizing, and/orstain removal, the composition comprising: (a) at least about 0.1%, byweight of the composition, of a halogenated salt having the formula(M)_(x)(X)_(y), wherein X can be Cl, Br, or I and wherein M can be ametal ion or cationic entity, and wherein x and y are chosen such thatthe salt can be charge balanced; (b) a component selected from the groupconsisting of a builder, suds suppressor, perfume, enzyme,bleach-scavenging agent, a metal-protecting agent, and mixtures thereof;and (c) an effective amount of an enzyme; and (d) an effective amount ofa thickening agent; wherein the liquid, liquitab, and/or gel compositioncan be optionally free of bleach. Another embodiment of the presentinvention relates to an ADD composition, wherein the composition doesnot contain chlorine bleach, oxygen bleach, or mixtures thereof.

[0159] The ADD compositions herein optionally comprise one or moreenzymes. If only one enzyme can be used, it can be preferably anamyolytic enzyme. Highly preferred for automatic dishwashing can be amixture of proteolytic enzymes and amyloytic enzymes. More generally,the enzymes to be incorporated include proteases, amylases, lipases,cellulases, and peroxidases, as well as mixtures thereof. Other types ofenzymes can also be included. They can be of any suitable origin, suchas vegetable, animal, bacterial, fungal and yeast origin. However, theirchoice can be governed by several factors such as pH-activity and/orstability optima, thermostability, stability versus active detergents,builders, etc. In this respect bacterial or fungal enzymes arepreferred, such as bacterial amylases and proteases, and fungalcellulases.

[0160] Enzymes are normally incorporated in the instant detergentcompositions at levels sufficient to provide a “cleaning-effectiveamount”. The term “cleaning-effective amount” refers to any amountcapable of producing a cleaning, stain removal or soil removal effect onsubstrates such as fabrics, tableware and the like. Since enzymes arecatalytic materials, such amounts can be very small. In practical termsfor current commercial preparations, typical amounts are up to about 5mg by weight, more typically about 0.01 mg to about 3 mg, of activeenzyme per gram of the composition. Stated otherwise, the compositionsherein will typically comprise from about 0.001% to about 6%, preferably0.01%-1% by weight of a commercial enzyme preparation. Protease enzymesare usually present in such commercial preparations at levels sufficientto provide from 0.005 to 0.1 Anson units (AU) of activity per gram ofcomposition. For automatic dishwashing purposes, it can be desirable toincrease the active enzyme content of the commercial preparations, inorder to minimize the total amount of non-catalytically active materialsdelivered and thereby improve spotting/filming results.

[0161] Suitable examples of proteases are the subtilisins which areobtained from particular strains of B. subtilis and B. licheniformis.Another suitable protease can be obtained from a strain of Bacillus,having maximum activity throughout the pH range of 8-12, developed andsold by Novo Industries A/S as ESPERASE®. The preparation of this enzymeand analogous enzymes can be described in British Patent SpecificationNo. 1,243,784 of Novo. Proteolytic enzymes suitable for removingprotein-based stains that are commercially available include those soldunder the tradenames ALCALASE® and SAVINASE® by Novo Industries A/S(Denmark). Other proteases include Protease A (see European PatentApplication 130,756, published Jan. 9, 1985) and Protease B (seeEuropean Patent Application Serial No. 87303761.8, filed Apr. 28, 1987,and European Patent Application 130,756, Bott et al, published Jan. 9,1985).

[0162] An especially preferred protease, referred to as “Protease D”, asdescribed in U.S. Pat. No. 5,679,630, Baeck, et al, and U.S. Pat. No.5,677,272, Ghosh, et al, both incorporated herein by reference. Amylasessuitable herein include, for example, α-amylases described in BritishPatent Specification No. 1,296,839 (Novo).

[0163] Engineering of enzymes (e.g., stability-enhanced amylase) forimproved stability, e.g., oxidative stability can be known. See, forexample, J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521.“Reference amylase” refers to a conventional amylase inside the scope ofthe amylase component of this invention. Further, stability-enhancedamylases, also within the invention, are typically compared to these“reference amylases”.

[0164] The present invention, in certain preferred embodiments, can makeuse of amylases having improved stability in detergents, especiallyimproved oxidative stability. A convenient absolute stabilityreference-point against which amylases used in these preferredembodiments of the instant invention represent a measurable improvementcan be the stability of TERMAMYL® in commercial use in 1993 andavailable from Novo Nordisk A/S. This TERMAMYL® amylase can be a“reference amylase”, and can be itself well-suited for use in the ADDcompositions of the invention.

[0165] Even more preferred amylases herein share the characteristic ofbeing “stability-enhanced” amylases, characterized, at a minimum, by ameasurable improvement in one or more of: oxidative stability, e.g., tohydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH9-10; thermal stability, e.g., at common wash temperatures such as about60° C.; or alkaline stability, e.g., at a pH from about 8 to about 11,all measured versus the above-identified reference-amylase. Preferredamylases herein can demonstrate further improvement versus morechallenging reference amylases, the latter reference amylases beingillustrated by any of the precursor amylases of which preferred amylaseswithin the invention are variants. Such precursor amylases canthemselves be natural or be the product of genetic engineering.Stability can be measured using any of the art-disclosed technicaltests. See references disclosed in WO 94/02597.

[0166] In general, stability-enhanced amylases respecting the preferredembodiments of the invention can be obtained from Novo Nordisk A/S, orfrom Genencor International. Preferred amylases herein have thecommonality of being derived using site-directed mutagenesis from one ormore of the Baccillus amylases, especialy the Bacillus alpha-amylases,regardless of whether one, two or multiple amylase strains are theimmediate precursors.

[0167] Such amylases are non-limitingly illustrated by the following:

[0168] (i) An amylase according to the hereinbefore incorporatedWO/94/02597, Novo Nordisk A/S, published Feb. 3, 1994, as furtherillustrated by a mutant in which substitution can be made, using alanineor threonine (preferably threonine), of the methionine residue locatedin position 197 of the B. licheniformis alpha-amylase, known asTERMAMYL®, or the homologous position variation of a similar parentamylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus;

[0169] (ii) Stability-enhanced amylases as described by GenencorInternational in a paper entitled “Oxidatively Resistant alpha-Amylases”presented at the 207th American Chemical Society National Meeting, Mar.13-17 1994, by C. Mitchinson. Therein it was noted that bleaches inautomatic dishwashing detergents inactivate alpha-amylases but thatimproved oxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8,15,197,256,304,366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE® and SUNLIGHT®;

[0170] (iii) Particularly preferred herein are amylase variants havingadditional modification in the immediate parent available from NovoNordisk A/S. These amylases do not yet have a tradename but are thosereferred to by the supplier as QL37+M197T.

[0171] Any other oxidative stability-enhanced amylase can be used, forexample as derived by site-directed mutagenesis from known chimeric,hybrid or simple mutant parent forms of available amylases.

[0172] A wide range of enzyme materials and means for theirincorporation into synthetic detergent compositions are also disclosedin U.S. Pat. No. 3,553,139, issued Jan. 5, 1971 to McCarty et al.Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al,issued Jul. 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes, issuedMar. 26, 1985, and in the above incorporated U.S. Pat. No. 6,143,707,Trinh et al, issued Nov. 7, 2000. Enzymes for use in detergents can bestabilized by various techniques. Enzyme stabilization techniques aredisclosed and exemplified in U.S. Pat. No. 3,600,319, issued Aug. 17,1971 to Gedge, et al, and European Patent Application Publication No. 0199 405, Application No. 86200586.5, published Oct. 29, 1986, Venegas.Enzyme stabilization systems are also described, for example, in U.S.Pat. No. 3,519,570.

[0173] (d) Chelating Agents

[0174] The compositions herein can also optionally contain one or moretransition-metal selective sequestrants, “chelants” or “chelatingagents”, e.g., iron and/or copper and/or manganese chelating agents.Chelating agents suitable for use herein can be selected from the groupconsisting of aminocarboxylates, phosphonates (especially theaminophosphonates), polyfunctionally-substituted aromatic chelatingagents, and mixtures thereof. Without intending to be bound by theory,it can be believed that the benefit of these materials can be due inpart to their exceptional ability to control iron, copper and manganesein washing solutions which are known to decompose hydrogen peroxideand/or bleach activators; other benefits include inorganic filmprevention or scale inhibition. Commercial chelating agents for useherein include the DEQUEST® series, and chelants from Monsanto, DuPont,and Nalco, Inc.

[0175] Aminocarboxylates useful as optional chelating agents are furtherillustrated by ethylenediaminetetracetates,N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates,ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal,ammonium, and substituted ammonium salts thereof. In general, chelantmixtures can be used for a combination of functions, such as multipletransition-metal control, long-term product stabilization, and/orcontrol of precipitated transition metal oxides and/or hydroxides.

[0176] Polyfunctionally-substituted aromatic chelating agents are alsouseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedcan 21, 1974, to Connor et al. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

[0177] A highly preferred biodegradable chelator for use herein can beethylenediamine disuccinate (“EDDS”), especially (but not limited to)the [S,S] isomer as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987,to Hartman and Perkins. The trisodium salt can be preferred though otherforms, such as magnesium salts, can also be useful.

[0178] Aminophosphonates are also suitable for use as chelating agentsin the compositions of the invention when at least low levels of totalphosphorus are acceptable in detergent compositions, and include theethylenediaminetetrakis (methylenephosphonates) and thediethylenetriaminepentakis (methylene phosphonates). Preferably, theseaminophosphonates do not contain alkyl or alkenyl groups with more thanabout 6 carbon atoms.

[0179] If utilized, chelating agents or transition-metal-selectivesequestrants will preferably comprise from about 0.001% to about 10%,more preferably from about 0.05% to about 1% by weight of thecompositions herein.

[0180] One embodiment of the present invention relates to an ADDcomposition comprising a chelant selected from the group consisting ofEDTA, tetraacetyl ethylene diamine (TAED), EDDS, aminophosphonates,aminocarboxylates, carboxylatephosphonates, aluminosilicates,magnesioaluminosiliates, polyfunctionally-substituted aromatic chelatingagents, and mixtures thereof.

[0181] (e) Dispersant Polymer

[0182] Preferred ADD compositions herein can additionally contain adispersant polymer. When present, a dispersant polymer in the instantADD compositions can be typically at levels in the range from 0 to about25%, preferably from about 0.5% to about 20%, more preferably from about1% to about 8%, by weight of the ADD composition. Dispersant polymersare useful for improved filming performance of the present ADDcompositions, especially in higher pH embodiments, such as those inwhich wash pH exceeds about 9.5. Particularly preferred are polymerswhich inhibit the deposition of calcium carbonate or magnesium silicateon dishware.

[0183] Dispersant polymers suitable for use herein are furtherillustrated by the film-forming polymers described in U.S. Pat. No.4,379,080 (Murphy), issued Apr. 5, 1983. Suitable polymers arepreferably at least partially neutralized or alkali metal, ammonium orsubstituted ammonium (e.g., mono-, di- or triethanolammonium) salts ofpolycarboxylic acids. The alkali metal, especially sodium salts are mostpreferred. While the molecular weight of the polymer can vary over awide range, it preferably can be from about 1,000 to about 500,000, morepreferably can be from about 1,000 to about 250,000, and mostpreferably, especially if the ADD can be for use in North Americanautomatic dishwashing appliances, can be from about 1,000 to about5,000.

[0184] Other suitable dispersant polymers include those disclosed inU.S. Pat. Nos. 3,308,067, 4,530,766, 3,723,322, 3,929,107, 3,803,285,3,629,121, 4,141,841, and 5,084,535; EP Pat. No. 66,915,.

[0185] Copolymers of acrylamide and acrylate having a molecular weightof from about 3,000 to about 100,000, preferably from about 4,000 toabout 20,000, and an acrylamide content of less than about 50%,preferably less than about 20%, by weight of the dispersant polymer canalso be used.

[0186] Particularly preferred dispersant polymers are low molecularweight modified polyacrylate copolymers. Suitable low molecular weightpolyacrylate dispersant polymer preferably has a molecular weight ofless than about 15,000, preferably from about 500 to about 10,000, mostpreferably from about 1,000 to about 5,000. The most preferredpolyacrylate copolymer for use herein has a molecular weight of about3,500 and can be the fully neutralized form of the polymer comprisingabout 70% by weight acrylic acid and about 30% by weight methacrylicacid.

[0187] Other dispersant polymers useful herein include the polyethyleneglycols and polypropylene glycols having a molecular weight of fromabout 950 to about 30,000 which can be obtained from the Dow ChemicalCompany of Midland, Mich.

[0188] Yet other dispersant polymers useful herein include the cellulosesulfate esters such as cellulose acetate sulfate, cellulose sulfate,hydroxyethyl cellulose sulfate, methylcellulose sulfate, andhydroxypropylcellulose sulfate. Sodium cellulose sulfate can be the mostpreferred polymer of this group. Yet another group of acceptabledispersants are the organic dispersant polymers, such as polyaspartate.

[0189] One embodiment of the present invention relates to an ADDcomposition comprising a dispersant polymer selected from the groupconsisting of poly (acrylic/allyl alcohol), poly (acrylic/maleic), poly(a-hydroxyacrylic acid), poly (tetramathylene-1,2-dicarbocylic acid),poly (4-methocy-tetramethylene-1,2-tetramethylene-1,2-dicarbocylicacid), polyacrylates, acrylic acid/maleic acid copolymers,polyalkyleneglycols, polyaminoacids, carboxyalkylcelluloses, alkylatedor hydroxyalkylated celluloses, ether hydroxypolycarboxylates,polyvinylpyrrolidone, polyvinylpyridine-N-oxide,poly(vinylpyrrolidone)-co-poly(vinylimidazole), polydimethylsiloxanes,polydimethylsiloxanes, trisiloxanes with pendant polyethylene,polyethylene/polypropylene sidechains, water soluble salts, andcombinations thereof.

[0190] (c) Thickeners

[0191] The physical stability of the liquid or gel product can beimproved, and the thickness of the product can be altered, by theaddition of a cross-linking thickener to the liquid or gel detergentproduct as a thixotropic thickener.

[0192] Thickeners for use herein include those selected from clay,polycarboxylates, such as Polygel®, gums, carboxymethyl cellulose,polyacrylates, and mixtures thereof. The preferred clay type herein hasa double-layer structure. The clay can be naturally occurring, e.g.,Bentonites, or artificially made, e.g., Laponite®. Laponite® can besupplied by Southern Clay Products, Inc. See The Chemistry and Physicsof Clays, Grimshaw, 4^(th) ed., 1971, pages 138-155, Wiley-Interscience.

[0193] One embodiment of the present invention relates to an ADDcomposition comprising a nanoparticle and/or functional colloidalparticle selected from the group consisting of: (a) inorganic metaloxides, natural clays, synthetic clays and mixtures thereof; (b)synthetic clays selected from the group consisting of kaolinite,montmorillinite/smectite, smectite, hectorite, synthetic flurohectorite,illite, variants and isomorphous substitutions of the synthetic claygroups and mixtures thereof; and (c) synthetic clays selected from thegroup consisting of layered hydrous silicate, layered hydrous aluminumsilicate, fluorosilicate, mica-montmorillonite, hydrotalcite, lithiummagnesium silicate, lithium magnesium fluorosilicate and mixturesthereof.

[0194] (d) Functionalized Surface Molecules

[0195] The functionalized surface molecule of the present invention canbe present in the composition to provide hydrophilic or hydrophobiccharacter to the composition, to anchor and/or enhance surfaceadsorption of the tableware, and/or to provide water-affinity to treatedtableware.

[0196] One embodiment of the present invention relates to an ADDcomposition comprising a functionalized surface molecule or componentand/or compound selected from the group consisting of monomericmaterials, polymers, copolymers and mixtures thereof, wherein at leastone segment and/or group of the monomeric material and/or polymer cancomprise functionality selected from the group consisting of providinghydrophilic or hydrophobic character to the monomeric material and/orpolymer, anchoring and/or enhancing adsorption on solid surfaces,providing water-affinity to the monomeric material and/or polymer, andcombinations thereof.

[0197] (e) pH Adjusting Components

[0198] The above liquid or gel detergent product can be preferably lowfoaming, readily soluble in the washing medium and most effective at pHvalues best conducive to improved cleaning performance, such as in arange of desirably from about pH 6.5 to about pH 12.5, and preferablyfrom about pH 7.0 to about pH 12.0, more preferably from about pH 8.0 toabout pH 12.0. Preferably the pH can be less than about 10.0 for betterenzyme stability, most preferably less than about 9.0. The pH adjustingcomponents are desirably selected from sodium or potassium hydroxide,sodium or potassium carbonate or sesquicarbonate, sodium or potassiumsilicate, boric acid, sodium or potassium bicarbonate, sodium orpotassium borate, and mixtures thereof. NaOH or KOH are the preferredingredients for increasing the pH to within the above ranges. Otherpreferred pH adjusting ingredients are sodium carbonate, potassiumcarbonate, and mixtures thereof.

[0199] (f) Organic Solvent

[0200] One embodiment of the present invention relates to an ADDcomposition comprising an organic solvent selected from the groupconsisting of low molecular weight aliphatic or aromatic alcohols, lowmolecular weight alkylene glycols, low molecular weight alkylene glycolethers, low molecular weight esters, low molecular weight alkyleneamines, low molecular weight alkanolamines, and mixtures thereof.

[0201] (g) Bleach, Bleach, Bleach Catalyst And/Or Bleach Activator

[0202] One embodiment of the present invention relates to an ADDcomposition comprising a bleach, bleach catalyst and/or bleach activatorcan be selected from the group consisting of benzoyl peroxide,6-phthalimidoperoxyhexanoic acid, 6-nonylamino-6-oxoperoxycaproic acid,tetraacetyl ethylene diamine, benzoylcaprolactam,nonanoyloxybenzenesulphonate (NOBS), decanoyloxybenzenesulphonate,(6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, magnesium monoperoxyphthalate,quaternary substituted bleach activators, and mixtures thereof.

[0203] (h) Electrochemically-Activated Pro-Benefit Agent

[0204] Another embodiment of the present invention relates to an ADDcomposition comprising an electrochemically-activated pro-benefit agentselected from the group consisting of pro-perfume, pro-oxidant,pro-reductant, pro-surface active agent, pro-glass care agent, andmixtures thereof, wherein when the electrochemically-activatedpro-benefit agent is exposed to at least one electrochemical cell itundergoes oxidation and/or reduction and can be thereby converted intoan active agent which provides a treatment benefit to tableware uponcontact with the tableware, and wherein the benefit can be selected fromthe group consisting of cleaning, aesthetic, disinfecting,stain-removal, dish-care, and combinations thereof.

[0205] (i) Moisture Content

[0206] Since ADD compositions herein can contain water-sensitiveingredients or ingredients which can co-react when brought together inan aqueous environment, it can be desirable to keep the free moisturecontent of the ADDs at a minimum, e.g., 7% or less, preferably 4% orless of the ADD; and to provide packaging which can be substantiallyimpermeable to water and carbon dioxide. Coating measures have beendescribed herein to illustrate a way to protect the ingredients fromeach other and from air and moisture. Plastic bottles, includingrefillable or recyclable types, as well as conventional barrier cartonsor boxes are another helpful means of assuring maximum shelf-storagestability. As noted, when ingredients are not highly compatible, it canfurther be desirable to coat at least one such ingredient with alow-foaming nonionic surfactant for protection. There are numerous waxymaterials which can readily be used to form suitable coated particles ofany such otherwise incompatible components; however, the formulatorprefers those materials which do not have a marked tendency to depositor form films on dishes including those of plastic construction.

[0207] One embodiment of the present invention relates to an ADDcomposition, wherein the composition can be present in the form selectedfrom the group consisting of liquid, gel, tablet, powder, water-solublepouch, and mixtures thereof.

[0208] Method for Treating Soiled Tableware

[0209] The present invention also relates to a method of treatingtableware in an automatic dishwashing appliance comprising anelectrochemical cell and/or electrolytic device that results in improvedtableware cleaning, sanitizing, and/or stain removal, the methodcomprising the steps of: (a) placing tableware in need of treatment inthe appliance; (b) providing an automatic dishwashing compositioncomprising a component selected from the group consisting of halogenatedsalt, phosphate, silicate, suds suppressor, perfume, bleach-scavengingagent, metal-protecting agent, and mixtures thereof, during a washand/or a rinse cycle in the appliance; (c) passing an aqueouselectrolytic solution through the electrochemical cell to generate atleast some electrolyzed water in the wash and/or rinse liquor of theappliance; and (d) contacting the tableware with the electrolyzed water.

[0210] This invention also encompases a method of washing tableware in adomestic or commercial automatic dishwashing appliance, comprisingtreating the soiled tableware in an automatic dishwasher with an aqueousbath comprising the above ADD composition.

[0211] This invention also encompases a method for cleaning, sanitizingand removing stains of soiled tableware comprising use of a separatecomposition in conjunction with electrolyzed water, such as at least oneproduct selected from the group consisting of a solid electrolysisprecursor compound of low water solubility, an electrolysis precursorcompound containing a matrix of low water solubility, and mixturesthereof, for treatment, pre-treatment, or post-treatment of tableware inan automatic dishwashing appliance can be used in conjunction with theelectrolysis process of the present invention.

[0212] The method of use can also incorporate the steps of providing anddispensing a bleach-scavenging agent to deactivate the halogenated mixedoxidants that were generated by the electrolysis process. The chlorinebleach-scavenging agent can be released subsequent to the period ofelectrolysis, or during one or more of the rinses to deactivate theabovementioned halogenated mixed oxidants.

[0213] The electrolyzed water that exits the electrolytic device of thisinvention can effectively disinfect and/or sanitize the aqueouselectrolytic solution comprising tap water, wash and/or rinse liquorsolution, recirculated wash and/or rinse liquor, and mixtures thereof,making the aqueous electrolytic solution useful for treating tablewarein automatic dishwashing appliances by providing cleaning, sanitization,and stain removal benefits in both commercial, as well as, inresidential applications. The attached, integrated, recirculatingelectrolytic device of the automatic dishwashing appliance can be usedfor cleaning, sanitization, and stain removal tableware in all types ofapplications.

[0214] Though recirculation of the wash and/or rinse liquor provides forcontinuous production of newly electrolyzed halogenated mixed oxidantsthat will be available immediately during specific times of the washand/or rinse cycles, it can be highly preferred to use the electrolyzedelectrolytic solution immediately after the electrolysis, since thebeneficial biocidal halogenated mixed oxidants have a short life span.Preferably, the aqueous electrolytic solution, when used fordisinfection and/or sanitization or sterilization, can be used withinabout 15 minutes, preferably within about 5 minutes, more preferablywithin about 1 minute, and most preferably almost immediately, afterelectrolysis.

[0215] One embodiment of the present invention relates to a method oftreating tableware in an automatic dishwashing appliance comprising anelectrochemical cell and/or electrolytic device that results in improvedtableware cleaning, sanitizing, and/or stain removal, the methodcomprising the steps of: (a) placing tableware in need of treatment inthe appliance; (b) providing an automatic dishwashing compositioncomprising a component selected from the group consisting of halogenatedsalt, builder, suds suppressor, perfume, bleach-scavenging agent,metal-protecting agent, and mixtures thereof, during a wash and/or arinse cycle in the appliance; (c) passing an aqueous electrolyticsolution through the electrochemical cell and/or electrolytic device togenerate at least some electrolyzed water in the wash and/or rinseliquor of the appliance; and (d) contacting the tableware with theelectrolyzed water.

[0216] Another embodiment of the present invention relates to a methodfurther can comprise the step of providing the composition for anadditional and/or separate dispensing during the wash and/or rinsecycles in the appliance after the step of initially contacting thetableware with the electrolyzed water. After the step of initiallycontacting the tableware with the electrolyzed water, the method canalso further comprise steps of providing an ADD composition comprising acomponent selected from the group consisting of bleach-scavenging agent,metal-protecting agent, and mixtures thereof, and subsequentlycontacting the tableware with a wash and/or rinse liquor comprising thecomposition. The method can further comprise repeating all and/orindividual steps until the tableware needing treatment can be treated Itcan be preferred that when the composition comprising bleach-scavengingagent, metal-protecting agent, and mixtures thereof, can be provided, nofurther electrolyzed water comes into contact with the tableware.

[0217] Another embodiment of the present invention relates to a method,wherein the builder can be selected from the group consisting ofphosphate, phosphate oligomers or polymers and salts thereof, silicateoligomers or polymers and salts thereof, aluminosilicates,magnesioaluminosiliates, citrate, and mixtures thereof. The compositioncan further comprise a chelant selected from the group consisting ofEDTA, tetraacetyl ethylene diamine (TAED), EDDS, aminophosphonates,aminocarboxylates, carboxylatephosphonates, aluminosilicates,magnesioaluminosiliates, polyfunctionally-substituted aromatic chelatingagents, and mixtures thereof.

[0218] Another embodiment of the present invention relates to a method,wherein the anti-corrosion agents and/or anti-tarnishing agents comprisea compound selected from the group consisting of sodium silicate,magnesium silicate, benzotriazole, fatty acid salts of aluminum, andmixtures thereof.

[0219] Another embodiment of the present invention relates to a method,wherein the composition further can comprise a dispersant polymerselected from the group consisting of poly (acrylic/allyl alcohol), poly(acrylic/maleic), poly (a-hydroxyacrylic acid), poly(tetramathylene-1,2-dicarbocylic acid), poly(4-methocy-tetramethylene-1,2-tetramethylene-1,2-dicarbocylic acid),polyacrylates, acrylic acid/maleic acid copolymers, polyalkyleneglycols,polyaminoacids, carboxyalkylcelluloses, alkylated or hydroxyalkylatedcelluloses, ether hydroxypolycarboxylates, polyvinylpyrrolidone,polyvinylpyridine-N-oxide,poly(vinylpyrrolidone)-co-poly(vinylimidazole), polydimethylsiloxanes,polydimethylsiloxanes, trisiloxanes with pendant polyethylene,polyethylene/polypropylene sidechains, water soluble salts, andcombinations thereof.

[0220] Another embodiment of the present invention relates to a method,wherein the composition can comprise a surfactant can be selected fromthe group consisting of anionic surfactants, cationic surfactants,nonionic surfactants, amphoteric surfactants, ampholytic surfactants,zwitterionic surfactants, and mixtures thereof.

[0221] Another embodiment of the present invention relates to a method,wherein the composition can comprise a nanoparticle and/or functionalcolloidal particle selected from the group consisting of: (a) inorganicmetal oxides, natural clays, synthetic clays and mixtures thereof; (b)synthetic clays selected from the group consisting of kaolinite,montmorillinite/smectite, smectite, hectorite, synthetic flurohectorite,illite, variants and isomorphous substitutions of the synthetic claygroups and mixtures thereof; and (c) synthetic clays selected from thegroup consisting of layered hydrous silicate, layered hydrous aluminumsilicate, fluorosilicate, mica-montmorillonite, hydrotalcite, lithiummagnesium silicate, lithium magnesium fluorosilicate and mixturesthereof.

[0222] Another embodiment of the present invention relates to a method,wherein the composition the functionalized surface molecule can comprisea component and/or compound selected from the group consisting ofmonomeric materials, polymers, copolymers and mixtures thereof, whereinat least one segment and/or group of the monomeric material and/orpolymer can comprise functionality selected from the group consisting ofproviding hydrophilic or hydrophobic character to the monomeric materialand/or polymer, anchoring and/or enhancing adsorption on solid surfaces,providing water-affinity to the monomeric material and/or polymer, andcombinations thereof.

[0223] Another embodiment of the present invention relates to a method,wherein the composition(s) do not contain chlorine bleach, oxygenbleach, and mixtures thereof.

[0224] Another embodiment of the present invention relates to a method,wherein the composition can comprise NaCl, KCl, and mixtures thereof, ata level of greater than about 0.1%, preferably at a level greater thanabout 0.5% by weight of the composition, more preferably at a level ofgreater than about 1% by weight of the composition. And most preferablyat a level of greater than about 2%, by weight of the composition.

[0225] Another embodiment of the present invention relates to a method,wherein the composition can comprise an organic solvent selected fromthe group consisting of low molecular weight aliphatic or aromaticalcohols, low molecular weight alkylene glycols, low molecular weightalkylene glycol ethers, low molecular weight esters, low molecularweight alkylene amines, low molecular weight alkanolamines, and mixturesthereof.

[0226] Another embodiment of the present invention relates to a method,wherein the composition can comprise a suds suppressor selected from thegroup consisting of low-foaming nonionic surfactants, low-foamingnonionic surfactants with a cloud point below about 30° C., alkoxylatesor mixed alkoxylates of linear fatty alcohols, alkoxylates or mixedalkoxylates of alkylphenols, block co-polymers of ethylene and propyleneglycol, C_(9/11)EO₈-yclohexyl acetal alkyl capped nonionic,C₁₁EO₇-n-butyl acetal, C_(9/11)EO₈-2-ethylhexyl acetal, C₁₁EO₈-pyranyl,alcohol alkoxylate, and mixtures thereof.

[0227] Another embodiment of the present invention relates to a method,wherein the composition can comprise a bleach, bleach catalyst and/orbleach activator can be selected from the group consisting of benzoylperoxide, 6-phthalimidoperoxyhexanoic acid,6-nonylamino-6-oxoperoxycaproic acid, tetraacetyl ethylene diamine,benzoylcaprolactam, nonanoyloxybenzene-sulphonate (NOBS),decanoyloxybenzenesulphonate, (6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, magnesium monoperoxyphthalate,quaternary substituted bleach activators, and mixtures thereof.

[0228] Another embodiment of the present invention relates to a method,wherein the composition can comprise a bleach-scavenging agent selectedfrom the group consisting of perborate, percarbonate, ascorbic acid orderivatives thereof, carbamate, ammonium, sulfite, bisulfite, aluminumtristearate, sodium silicate, benzotriazole, amines, amino acids, andmixtures thereof.

[0229] Another embodiment of the present invention relates to a method,wherein the composition can comprise an electrochemically-activatedpro-benefit agent can comprise a compound selected from the groupconsisting of pro-perfume, pro-oxidant, pro-reductant, pro-surfaceactive agent, pro-glass care agent, and mixtures thereof, wherein whenthe electrochemically-activated pro-benefit agent is exposed to at leastone electrochemical cell it undergoes oxidation and/or reduction and canbe thereby converted into an active agent which provides a treatmentbenefit to tableware upon contact with the tableware, and wherein thebenefit can be selected from the group consisting of cleaning,aesthetic, disinfecting, stain-removal, dish-care, and combinationsthereof.

[0230] Another embodiment of the present invention relates to a method,wherein the composition can comprise an electrode maintenance and/ordescaling agents can be selected from the group consisting of citricacid, acetic acid, and mixtures thereof.

[0231] Another embodiment of the present invention relates to a method,wherein the composition can comprise an electrolytic device comprisingat least one of the features selected from the group consisting of (a) anon-partitioned electrochemical cell; (b) at least one disposable and/orreplaceable electrochemical cell component; (c) a recirculating systemallowing for wash and/or rinse liquor to continuously circulate and/orrecirculate through the electrolytic device, into the bulk wash or rinseliquor contained in the appliance, and back through the device; (d) anelectrochemical cell comprising a cathode of stainless steel, an anodeof titanium coated or layered with at least one of the materialsselected from the group consisting of platinum, ruthenium, iridium, andoxides, alloys, and mixtures thereof, (e) a gap between the at least onepair of electrodes having a gap spacing between about 0.1 mm to about0.5 mm, (f) an operating voltage of the electrolytic device and/orelectrochemical cell between about 1.5 and about 220 volts; andcombination thereof.

[0232] Another embodiment of the present invention relates to a method,wherein the composition can be used in the wash and/or rinse cycle ofthe appliance at temperatures from about 120 degrees F. and below.

[0233] Article of Manufacture

[0234] The present invention relates to an article of manufacture for anautomatic dishwashing appliance comprising: (a) a package; (b) areplacement product comprising a component selected from electrolyticsolution comprising halogen ions, halogenated salts having the formula(M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y) wherein X can be Cl, Br, or I andwherein M can be a metal ion or cationic entity and wherein x and y arechosen such that the salt can be charge balanced, electrolysis precursorcompound, a halogenated salt with low water solubility, a halogenatedsalt contained within a medium for controlled release, and mixturesthereof, (c) optionally, a replacement a porous basket comprising theproduct for dispensing; and (c) information in association with thepackage comprising instructions to insert the replacement componentsand/or the a porous basket in the appliance and/or the electrolyticdevice.

[0235] The present invention also relates to an article of manufacture,wherein the replacement product can be in the form such that once placedinside a dishwashing appliance it provides a controlled release of theelectrolysis precursor compound into the wash and/or rinse liquorsduring operation of the automatic dishwasher over a period of severalweeks or months of regular household and/or commercial use.

[0236] Commercial Automatic Dishwashing Appliance

[0237] One embodiment of the present invention comprises ADD compositionand/or method of using said composition in a commercial dishwasherappliance selected from the group consisting of conveyor-low-temperaturetype, cabinet-low-temperature type, and combinations thereof.

[0238] Composition of Matter

[0239] The present invention relates to an ADD composition of matterconsisting essentially of the in the wash and/or rinse liquor of anautomatic dishwashing appliance comprising an electrochemical celland/or electrolytic device for improved tableware cleaning, sanitizing,and/or stain removal, the composition of matter comprising: (a) at leastsome electrolyzed water comprising halogenated mixed oxidants; (b) anADD composition comprising a compound selected from the group consistingof a halogenated salts, halogenated salt with low water solubility,builder, suds suppressor, perfume, enzyme, bleach-scavenging agent, ametal-protecting agent, and mixtures thereof, (c) optionally, an ADDcomposition comprising a compound selected from the group consisting ofan electrolytic composition comprising halogen ions, an electrolyticcomposition comprising halogenated salts having the formula(M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y) wherein X can be Cl, Br, or I andwherein M can be a metal ion or cationic entity and wherein x and y arechosen such that the salt can be charge balanced, an electrolysisprecursor compound, a halogenated salt with low water solubility, anelectrolysis precursor compound contained within a medium for controlledrelease, and mixtures thereof; and (d) optionally, adjunct ingredients.

[0240] Another embodiment of the present invention relates to acomposition of matter, wherein the operating temperature during the washand/or rinse cycle(s) of said appliance is less than about 120° F. Thus,the composition of matter comprises a water temperature less than about120° F.

EXAMPLES

[0241] Examples of formulations according to the present invention areas follows. All ingredients are expressed as weight % of the totalformula composition. A B C D E F G H Builder¹ 25 25 30 30 30 30 20 20Na2CO3 25 25 10 10 — — — — Silicate 10 10 8 8 10 12 — — Enzymes² 1.0 2.02.0 2.0 1.0 2.0 3.0 4.0 NaOH — — — — 1.0 — 1.0 1.0 Dispersant — 0.5 1.01.0 0.5 — 0.5 0.5 Polymer³ Suds 1.0 1.0 1.5 1.5 1.0 1.5 2.0 2.0suppressor⁴ Halogenated 0.5 1.0 5.0 7.0 0.5 1.0 5.0 5.0 salt⁵ Thickener⁶— — — — 0.5 0.5 0.7 0.7 HEDP⁷ — 0.5 — — — 0.5 — — Filler and balancebalance balance Balance balance balance balance balance adjuncts⁸

[0242] Further examples of formulations according to the presentinvention are as follows. All ingredients are expressed as weight % ofthe total formula composition. I J K L builder¹ 5 10 5 — solvent² 10 1010 10 nonionic 15 15 20 10 surfactant³ Polymer⁴ — — 0.5 — HEDP⁵ — 1.0 —— NaOH — — — 0.2 hydrotrope⁶ 5 10 — — Halogenated 1.0 2.0 10 5.0 salt⁷Filler and Balance balance balance Balance adjuncts⁸

What is claimed is:
 1. An automatic dishwashing composition for treatingtableware in an automatic dishwashing appliance comprising anelectrochemical cell for improved tableware cleaning, sanitizing, and/orstain removal, said composition comprising: (a) a halogen dioxide salthaving the formula (M)_(x)(XO₂)_(y), wherein X is Cl, Br, or I andwherein M is a metal ion or cationic entity, and wherein x and y arechosen such that the salt is charge balanced; and (b) a componentselected from the group consisting of a builder, suds suppressor,perfume, enzyme, bleach-scavenging agent, a metal-protecting agent, andmixtures thereof; and (c) optionally, at least one adjunct ingredient;wherein said composition is free of bleach.
 2. A composition accordingto claim 1, wherein said halogen dioxide salt comprises a salt selectedfrom the group consisting of NaClO₂, KClO₂, and mixtures thereof, andwherein said halogen dioxide salt is present at a level of greater thanabout 0.1% by weight of the composition.
 3. A composition according toclaim 2, wherein said salt is present at a level of greater than about0.5% by weight of the composition.
 4. A composition according to claim2, wherein said salt is present at a level of greater than about 1.0% byweight of the composition.
 5. A composition according to claim 1,wherein said halogen dioxide salt is in a form selected from the groupcharacterized by low water solubility, contained within a medium forcontrolled release, and combinations thereof.
 6. A composition accordingto claim 5, wherein said controlled release form of said halogen dioxidesalt comprises a form such that once placed inside a dishwashingappliance it provides a controlled release of steady levels of halogendioxide salts into the wash and/or rinse liquors during operation of anautomatic dishwasher over a period of from 1 day to 365 days of regularhousehold and/or commercial use.
 7. A composition according to claim 6,wherein said composition is housed in a permeable container such that itis conveniently located inside a typical automatic dishwasher withoutinterfering with said dishwasher's normal usage; wherein said containercomprises a material selected from the group consisting of glass,plastic, ceramic, metal, and combinations thereof.
 8. A compositionaccording to claim 1, wherein said wherein said bleach-scavenging agentcomprises a compound selected from the group consisting of perborate,percarbonate, ascorbic acid or derivatives thereof, carbamate, ammonium,sulfite, bisulfite, aluminum tristearate, sodium silicate,benzotriazole, amines, amino acids, and mixtures thereof.
 9. Acomposition according to claim 1 further comprising at least one adjunctingredient, wherein said adjunct ingredient is selected from the groupconsisting of nanoparticles, functionalized surface molecules, polymers,surfactants, co-surfactants, metal ions, proteins, dyes, acids, bases,organic solvents, enzymes, enzyme stabilizing systems, chelants, opticalbrighteners, soil release agents, wetting agents, dispersants, bloomingperfumes, colorants, filler salts, hydrotropes, perservatives,anti-oxidants, germicides, fungicides, color speckles, silvercare,anti-tarnishing agents, alkalinity sources, solubilizing agents,carriers, electrode maintenance and/or descaling agents, processingaids, pigments, and pH control agents, bleaching agent, bleachactivators, bleach catalysts and mixtures thereof.
 10. A compositionaccording to claim 1 that does not contain chlorine bleach, oxygenbleach, or mixtures thereof.
 11. A composition according to claim 2,wherein said builder is selected from the group consisting of phosphate,phosphate oligomers or polymers and salts thereof, silicate oligomers orpolymers and salts thereof, aluminosilicates, magnesioaluminosiliates,citrate, and mixtures thereof.
 12. A composition according to claim 11,further comprising a chelant selected from the group consisting of EDTA,tetraacetyl ethylene diamine (TAED), EDDS, aminophosphonates,aminocarboxylates, carboxylatephosphonates, alum inosi licates,magnesioalum inosi liates, polyfunctionally-substituted aromaticchelating agents, and mixtures thereof.
 13. A composition according toclaim 1, wherein said composition is present in the form selected fromthe group consisting of liquid, gel, tablet, powder, water-solublepouch, and mixtures thereof.
 14. A composition according to claim 9,wherein said perfume is from about 0.01% to about 5%, by weight, ablooming perfume composition, wherein said blooming perfume compositioncomprises from about 50% to about 99% of blooming perfume ingredientshaving a boiling point of less than about 260° C. and a ClogP of atleast about 3, and wherein said blooming perfume composition comprisingat least about 5 different blooming perfume ingredients, and from about0.5% to about 10% of base masking perfume ingredients having a boilingpoint of more than about 260° C. and a ClogP of at least about
 3. 15. Anautomatic dishwashing composition for treating tableware in an automaticdishwashing appliance comprising an electrochemical cell and/orelectrolytic device for improved tableware cleaning, sanitizing, and/orstain removal, said composition comprising: (a) at least about 0.1%, byweight of the composition, of a halogenated salt having the formula(M)_(x)(X)_(y), wherein X is Cl, Br, or I and wherein M is a metal ionor cationic entity, and wherein x and y are chosen such that the salt ischarge balanced; and (b) a component selected from the group consistingof a builder, suds suppressor, perfume, enzyme, bleach-scavenging agent,a metal-protecting agent, and mixtures thereof; and (c) optionally, atleast one adjunct ingredient; wherein said composition is free ofbleach.
 16. A composition according to claim 15, wherein saidhalogenated salt comprises a salt selected from the group consisting ofNaCl, KCl, and mixtures thereof, and wherein said salt is present at alevel of greater than about 0.1% by weight of the composition.
 17. Acomposition according to claim 16, wherein said salt is present at alevel of greater than about 0.5% by weight of the composition.
 18. Acomposition according to claim 16, wherein said salt is present at alevel of greater than about 1.0% by weight of the composition.
 19. Acomposition according to claim 15, wherein said halogenated salt is in aform selected from the group characterized by low water solubility,contained within a medium for controlled release, and combinationsthereof.
 20. A composition according to claim 19, wherein saidcontrolled release form of said salt comprises a form such that onceplaced inside a dishwashing appliance it provides a controlled releaseof steady levels of halogen dioxide salts into the wash and/or rinseliquors during operation of an automatic dishwasher over a period offrom 1 day to 365 days of regular household and/or commercial use.
 21. Acomposition according to claim 20, wherein said composition is housed ina permeable container such that it is conveniently located inside atypical automatic dishwasher without interfering with said dishwasher'snormal usage; wherein said container comprises a material selected fromthe group consisting of glass, plastic, ceramic, metal, and combinationsthereof.
 22. A composition according to claim 15, wherein said whereinsaid bleach-scavenging agent comprises a compound selected from thegroup consisting of perborate, percarbonate, ascorbic acid orderivatives thereof, carbamate, ammonium, sulfite, bisulfite, aluminumtristearate, sodium silicate, benzotriazole, amines, amino acids, andmixtures thereof.
 23. A composition according to claim 15 furthercomprising at least one adjunct ingredient, wherein said adjunctingredient is selected from the group consisting of nanoparticles,functionalized surface molecules, polymers, surfactants, co-surfactants,metal ions, proteins, dyes, acids, bases, organic solvents, enzymes,enzyme stabilizing systems, chelants, optical brighteners, soil releaseagents, wetting agents, dispersants, blooming perfumes, colorants,filler salts, hydrotropes, perservatives, anti-oxidants, germicides,fungicides, color speckles, silvercare, anti-tarnishing agents,alkalinity sources, solubilizing agents, carriers, electrode maintenanceand/or descaling agents, processing aids, pigments, and pH controlagents, bleaching agent, bleach activators, bleach catalysts andmixtures thereof.
 24. A composition according to claim 15 that does notcontain chlorine bleach, oxygen bleach, or mixtures thereof.
 25. Acomposition according to claim 16, wherein said builder is selected fromthe group consisting of phosphate, phosphate oligomers or polymers andsalts thereof, silicate oligomers or polymers and salts thereof,aluminosilicates, magnesioaluminosiliates, citrate, and mixturesthereof.
 26. A composition according to claim 25, further comprising achelant selected from the group consisting of EDTA, tetraacetyl ethylenediamine (TAED), EDDS, aminophosphonates, aminocarboxylates,carboxylatephosphonates, aluminosilicates, magnesioaluminosiliates,polyfunctionally-substituted aromatic chelating agents, and mixturesthereof.
 27. A composition according to claim 15, wherein saidcomposition is present in the form selected from the group consisting ofliquid, gel, tablet, powder, water-soluble pouch, and mixtures thereof.28. A composition according to claim 15, wherein said perfume is fromabout 0.01% to about 5%, by weight, a blooming perfume composition,wherein said blooming perfume composition comprises from about 50% toabout 99% of blooming perfume ingredients having a boiling point of lessthan about 260° C. and a ClogP of at least about 3, and wherein saidblooming perfume composition comprising at least about 5 differentblooming perfume ingredients, and from about 0.5% to about 10% of basemasking perfume ingredients having a boiling point of more than about260° C. and a ClogP of at least about
 3. 29. A liquid, liquitab, and/orgel automatic dishwashing composition for treating tableware in anautomatic dishwashing appliance comprising an electrochemical cell forimproved tableware cleaning, sanitizing, and/or stain removal, saidcomposition comprising: (a) at least about 0.1%, by weight of thecomposition, of a halogen dioxide salt and/or halogenated salt havingthe formula (M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y), wherein X is Cl, Br,or I and wherein M is a metal ion or cationic entity, and wherein x andy are chosen such that the salt is charge balanced; (d) a componentselected from the group consisting of a builder, suds suppressor,perfume, enzyme, bleach-scavenging agent, a metal-protecting agent, andmixtures thereof; and (b) an effective amount of an enzyme; and (e) aneffective amount of a thickening agent; and (f) optionally, at least oneadjunct ingredient; wherein said liquid, liquitab, and/or gelcomposition is free of bleach.
 30. A composition according to claim 29,wherein said salt is selected from the group consisting of NaClO₂,KClO₂, NaCl, KCl, and mixtures thereof, and wherein said salt is presentat a level of greater than about 0.1% by weight of the composition. 31.A composition according to claim 30, wherein said salt is present at alevel of greater than about 0.5% by weight of the composition.
 32. Acomposition according to claim 30, wherein said salt is present at alevel of greater than about 1.0% by weight of the composition.
 33. Acomposition according to claim 29, wherein said salt is in a formselected from the group characterized by low water solubility, containedwithin a medium for controlled release, and combinations thereof.
 34. Acomposition according to claim 33, wherein said controlled release formof said salt comprises a form such that once placed inside a dishwashingappliance it provides a controlled release of steady levels of halogendioxide salts into the wash and/or rinse liquors during operation of anautomatic dishwasher over a period of from 1 day to 365 days of regularhousehold and/or commercial use.
 35. A composition according to claim34, wherein said composition is housed in a permeable container suchthat it is conveniently located inside a typical automatic dishwasherwithout interfering with said dishwasher's normal usage; wherein saidcontainer comprises a material selected from the group consisting ofglass, plastic, ceramic, metal, and combinations thereof.
 36. Acomposition according to claim 29, wherein said wherein saidbleach-scavenging agent comprises a compound selected from the groupconsisting of perborate, percarbonate, ascorbic acid or derivativesthereof, carbamate, ammonium, sulfite, bisulfite, aluminum tristearate,sodium silicate, benzotriazole, amines, amino acids, and mixturesthereof.
 37. A composition according to claim 29 further comprising atleast one adjunct ingredient, wherein said adjunct ingredient isselected from the group consisting of nanoparticles, functionalizedsurface molecules, polymers, surfactants, co-surfactants, metal ions,proteins, dyes, acids, bases, organic solvents, enzymes, enzymestabilizing systems, chelants, optical brighteners, soil release agents,wetting agents, dispersants, blooming perfumes, colorants, filler salts,hydrotropes, perservatives, anti-oxidants, germicides, fungicides, colorspeckles, silvercare, anti-tarnishing agents, alkalinity sources,solubilizing agents, carriers, electrode maintenance and/or descalingagents, processing aids, pigments, and pH control agents, bleachingagent, bleach activators, bleach catalysts and mixtures thereof.
 38. Acomposition according to claim 29 that does not contain chlorine bleach,oxygen bleach, or mixtures thereof.
 39. A composition according to claim30, wherein said builder is selected from the group consisting ofphosphate, phosphate oligomers or polymers and salts thereof, silicateoligomers or polymers and salts thereof, aluminosilicates,magnesioaluminosiliates, citrate, and mixtures thereof.
 40. Acomposition according to claim 31, further comprising a chelant selectedfrom the group consisting of EDTA, tetraacetyl ethylene diamine (TAED),EDDS, aminophosphonates, aminocarboxylates, carboxylatephosphonates,aluminosilicates, magnesioaluminosiliates, polyfunctionally-substitutedaromatic chelating agents, and mixtures thereof.
 41. A compositionaccording to claim 29, wherein said enzyme is selected from the groupconsisting of amylase, protease, lipase, oxidase, and mixtures thereof.42. A composition according to claim 29, wherein said perfume is fromabout 0.01% to about 5%, by weight, a blooming perfume composition,wherein said blooming perfume composition comprises from about 50% toabout 99% of blooming perfume ingredients having a boiling point of lessthan about 260° C. and a ClogP of at least about 3, and wherein saidblooming perfume composition comprising at least about 5 differentblooming perfume ingredients, and from about 0.5% to about 10% of basemasking perfume ingredients having a boiling point of more than about260° C. and a ClogP of at least about
 3. 43. A method of treatingtableware in an automatic dishwashing appliance comprising anelectrochemical cell and/or electrolytic device that results in improvedtableware cleaning, sanitizing, and/or stain removal, said methodcomprising the steps of: (a) placing tableware in need of treatment insaid appliance; (b) providing an automatic dishwashing compositioncomprising a component selected from the group consisting of halogenatedsalt, builder, suds suppressor, perfume, bleach-scavenging agent,metal-protecting agent, and mixtures thereof, during a wash and/or arinse cycle in said appliance; (c) passing an aqueous electrolyticsolution through said electrochemical cell and/or electrolytic device togenerate at least some electrolyzed water in the wash and/or rinseliquor of said appliance; and (d) contacting said tableware with saidelectrolyzed water.
 44. A method according to claim 43 after step (c),said method further comprises step of providing said composition for anadditional and/or separate dispensing during the wash and/or rinsecycles in said appliance.
 45. A method according to claim 43 after step(d), said method further comprises steps of providing a compositioncomprising a component selected from the group consisting ofbleach-scavenging agent, metal-protecting agent, and mixtures thereof,and contacting said tableware with a wash and/or rinse liquor comprisingsaid composition.
 46. A method according to claim 43, said methodfurther comprises step of repeating steps (b) through (d) until thetableware needing treatment is treated
 47. A method according to claim45, wherein after said composition comprising bleach-scavenging agent,metal-protecting agent, and mixtures thereof, is provided, no furtherelectrolyzed water comes into contact with said tableware.
 48. A methodaccording to claim 43, wherein said builder is selected from the groupconsisting of phosphate, phosphate oligomers or polymers and saltsthereof, silicate oligomers or polymers and salts thereof,aluminosilicates, magnesioaluminosiliates, citrate, and mixturesthereof.
 49. A method according to claim 48, said composition furthercomprising a chelant selected from the group consisting of EDTA,tetraacetyl ethylene diamine (TAED), EDDS, aminophosphonates,aminocarboxylates, carboxylatephosphonates, aluminosilicates,magnesioaluminosiliates, polyfunctionally-substituted aromatic chelatingagents, and mixtures thereof.
 50. A method according to claim 43,wherein said anti-corrosion agents and/or anti-tarnishing agentscomprise a compound selected from the group consisting of sodiumsilicate, magnesium silicate, benzotriazole, fatty acid salts ofaluminum, and mixtures thereof.
 51. A method according to claim 43,wherein said composition further comprising a dispersant polymerselected from the group consisting of poly (acrylic/allyl alcohol), poly(acrylic/maleic), poly (a-hydroxyacrylic acid), poly(tetramathylene-1,2-dicarbocylic acid), poly(4-methocy-tetramethylene-1,2-tetramethylene-1,2-dicarbocylic acid),polyacrylates, acrylic acid/maleic acid copolymers, polyalkyleneglycols,polyaminoacids, carboxyalkylcelluloses, alkylated or hydroxyalkylatedcelluloses, ether hydroxypolycarboxylates, polyvinylpyrrolidone,polyvinylpyridine-N-oxide, poly(vinylpyrrol idone)-co-poly(vinylimidazole), polydimethylsiloxanes, polydimethylsiloxanes, trisiloxaneswith pendant polyethylene, polyethylene/polypropylene sidechains, watersoluble salts, and combinations thereof.
 52. A method according to claim43, said composition further comprising a surfactant is selected fromthe group consisting of anionic surfactants, cationic surfactants,nonionic surfactants, amphoteric surfactants, ampholytic surfactants,zwitterionic surfactants, and mixtures thereof.
 53. A method accordingto claim 43, said composition further comprising a nanoparticle and/orfunctional colloidal particle is selected from the group consisting of:a) inorganic metal oxides, natural clays, synthetic clays and mixturesthereof; b) synthetic clays selected from the group consisting ofkaolinite, montmorillinite/smectite, smectite, hectorite, syntheticflurohectorite, illite, variants and isomorphous substitutions of saidsynthetic clay groups and mixtures thereof; and c) synthetic claysselected from the group consisting of layered hydrous silicate, layeredhydrous aluminum silicate, fluorosilicate, mica-montmorillonite,hydrotalcite, lithium magnesium silicate, lithium magnesiumfluorosilicate and mixtures thereof.
 54. A method according to claim 53,wherein said functionalized surface molecule comprises a componentand/or compound selected from the group consisting of monomericmaterials, polymers, copolymers and mixtures thereof, wherein at leastone segment and/or group of said monomeric material and/or polymercomprises functionality selected from the group consisting of providinghydrophilic or hydrophobic character to said monomeric material and/orpolymer, anchoring and/or enhancing adsorption on solid surfaces,providing water-affinity to said monomeric material and/or polymer, andcombinations thereof.
 55. A method according to claim 43, wherein saidcomposition or compositions do not contain chlorine bleach, oxygenbleach, and mixtures thereof.
 56. A method according to claim 43,wherein said salt is selected from the group consisting of NaClO₂,KClO₂, NaCl, KCl, and mixtures thereof, and wherein said salt is presentat a level of greater than about 0.1% by weight of the composition. 57.A method according to claim 56, wherein said salt is present at a levelof greater than about 0.5% by weight of the composition.
 58. A methodaccording to claim 56, wherein said salt is present at a level ofgreater than about 1% by weight of the composition.
 59. A methodaccording to claim 43, wherein said composition further comprises anorganic solvent selected from the group consisting of low molecularweight aliphatic or aromatic alcohols, low molecular weight alkyleneglycols, low molecular weight alkylene glycol ethers, low molecularweight esters, low molecular weight alkylene amines, low molecularweight alkanolamines, and mixtures thereof.
 60. A method according toclaim 43, wherein said suds suppressor is selected from the groupconsisting of low-foaming nonionic surfactants, low-foaming nonionicsurfactants with a cloud point below about 30° C., alkoxylates or mixedalkoxylates of linear fatty alcohols, alkoxylates or mixed alkoxylatesof alkylphenols, block co-polymers of ethylene and propylene glycol,C_(9/11)EO₈-cyclohexyl acetal alkyl capped nonionic, C₁₁EO₇-n-butylacetal, C_(9/11)EO₈-2-ethylhexyl acetal, C₁₁EO₈-pyranyl, alcoholalkoxylate, and mixtures thereof.
 61. A method according to claim 43,wherein said composition further comprises a bleach, bleach catalystand/or bleach activator is selected from the group consisting of benzoylperoxide, ε-phthalimidoperoxyhexanoic acid,6-nonylamino-6-oxoperoxycaproic acid, tetraacetyl ethylene diamine,benzoylcaprolactam, nonanoyloxybenzenesulphonate (NOBS),decanoyloxybenzenesulphonate, (6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, magnesium monoperoxyphthalate,quaternary substituted bleach activators, and mixtures thereof.
 62. Amethod according to claim 43, wherein said bleach-scavenging agentcomprises a compound selected from the group consisting of perborate,percarbonate, ascorbic acid or derivatives thereof, carbamate, ammonium,sulfite, bisulfite, aluminum tristearate, sodium silicate,benzotriazole, amines, amino acids, and mixtures thereof.
 63. A methodaccording to claim 43, wherein said composition further comprises anelectrochemically-activated pro-benefit agent comprises a compoundselected from the group consisting of pro-perfume, pro-oxidant,pro-reductant, pro-surface active agent, pro-glass care agent, andmixtures thereof, wherein when said electrochemically-activatedpro-benefit agent is exposed to at least one electrochemical cell itundergoes oxidation and/or reduction and is thereby converted into anactive agent which provides a treatment benefit to tableware uponcontact with said tableware, and wherein said benefit is selected fromthe group consisting of cleaning, aesthetic, disinfecting,stain-removal, dish-care, and combinations thereof.
 64. A methodaccording to claim 63, wherein said electrode maintenance and/ordescaling agents is selected from the group consisting of citric acid,acetic acid, and mixtures thereof.
 65. A method according to claim 43wherein said electrolytic device comprises at least one of the featuresselected from the group consisting of (a) a non-partitionedelectrochemical cell; (b) at least one disposable and/or replaceableelectrochemical cell component; (c) a recirculating system allowing forwash and/or rinse liquor to continuously circulate and/or recirculatethrough said electrolytic device, into the bulk wash or rinse liquorcontained in said appliance, and back through said device; (d) anelectrochemical cell comprising a cathode of stainless steel, an anodeof titanium coated or layered with at least one of the materialsselected from the group consisting of platinum, ruthenium, iridium, andoxides, alloys, and mixtures thereof, (e) a gap between the said atleast one pair of electrodes having a gap spacing between about 0.1 mmto about 0.5 mm, (f) an operating voltage of said electrolytic deviceand/or electrochemical cell between about 1.5 and about 220 volts; andcombination thereof.
 65. A method according to claim 43 wherein said,wherein said composition is used in the wash and/or rinse cycle of saidappliance at temperatures below 120 degrees F. 66 An article ofmanufacture for an automatic dishwashing appliance comprising: (a) apackage; (b) a replacement product comprising a component selected fromelectrolytic solution comprising halogen ions, halogenated salts havingthe formula (M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y) wherein X is Cl, Br,or I and wherein M is a metal ion or cationic entity and wherein x and yare chosen such that the salt is charge balanced, electrolysis precursorcompound, a halogenated salt with low water solubility, a halogenatedsalt contained within a medium for controlled release, and mixturesthereof, (c) optionally, a replacement a porous basket comprising saidproduct for dispensing; and (d) information in association with saidpackage comprising instructions to insert said replacement productand/or said a porous basket in said appliance and/or said electrolyticdevice.
 66. An article of manufacture according to claim 65, whereinsaid replacement product is in the form such that once placed inside adishwashing appliance it provides a controlled release of saidelectrolysis precursor compound into the wash and/or rinse liquorsduring operation of said automatic dishwasher over a period of severalweeks or months of regular household and/or commercial use.
 67. Acomposition of matter consisting essentially of the wash and/or rinseliquor of an automatic dishwashing appliance comprising anelectrochemical cell and/or electrolytic device for improved tablewarecleaning, sanitizing, and/or stain removal, said composition of mattercomprising: (a) at least some electrolyzed water comprising halogenatedmixed oxidants; (b) a composition comprising a compound selected fromthe group consisting of a halogenated salt, builder, suds suppressor,perfume, enzyme, bleach-scavenging agent, a metal-protecting agent, andmixtures thereof; (c) optionally, a composition comprising a compoundselected from the group consisting of an electrolytic compositioncomprising halogen ions, an electrolytic composition comprisinghalogenated salts having the formula (M)_(x)(XO₂)_(y) and/or(M)_(x)(X)_(y) wherein X is Cl, Br, or I and wherein M is a metal ion orcationic entity and wherein x and y are chosen such that the salt ischarge balanced, an electrolysis precursor compound, a halogenated saltwith low water solubility, an electrolysis precursor compound containedwithin a medium for controlled release, and mixtures thereof; and (d)optionally, at least one adjunct ingredient.
 68. A composition of matteraccording to claim 67, wherein the operating temperature during the washand/or rinse cycle(s) of said appliance is less than about 120° F.
 69. Amethod according to claim 43, wherein said appliance is a commercialdishwasher selected from the group consisting ofconveyor-low-temperature type, cabinet-low-temperature type, andcombinations thereof.
 70. A liquid, liquitab, and/or gel automaticdishwashing composition for treating tableware in an automaticdishwashing appliance comprising an electrochemical cell for improvedtableware cleaning, sanitizing, and/or stain removal, said compositioncomprising: (a) at least about 0.5%, by weight of the composition, of asalt having the formula (M)_(x)(XO₂)_(y) and/or (M)_(x)(X)_(y), whereinX is F, Cl, Br, or I and wherein M is a metal ion or cationic entity,and wherein x and y are chosen such that the salt is charge balanced;(b) a component selected from the group consisting of a builder, sudssuppressor, perfume, enzyme, bleach-scavenging agent, a metal-protectingagent, and mixtures thereof; (c) an effective amount of a thickeningagent; and (d) optionally, at least one adjunct ingredient.